TWI253543B - Chemically amplified positive resist composition - Google Patents

Abstract

A chemically amplified positive resist composition contains as a base a carboxyl or phenolic hydroxyl group-containing resin soluble in aqueous alkaline solution, in which acid labile groups are incorporated into at least some of the hydrogen atoms on the carboxyl or phenolic hydroxyl groups so that the resin becomes insoluble or substantially insoluble in alkali, wherein the resin contains acid labile groups of at least two types, acid labile groups of one type are acetal or ketal groups, and acid labile groups of the other type are tertiary hydrocarbon groups or tertiary hydrocarbon group-containing substituents. The resist composition remains stable during vacuum standing after exposure to electron beams or soft x-rays, leaves minimal footings on chromium substrates, has an excellent sensitivity and resolution, and is thus suited as a micropatterning material for use in the processing of mask substrates.

Description

1253543 Economic, Intellectual Property Office, Staff and Consumer Cooperatives Printed A7 B7 V. Invention Description (T) Technical Field of the Invention The present invention relates to an electron beam or soft X-ray exposure processing technique, and the vacuum is also less placed after light. A novel reinforced chemical positive resist material having only a very small curl [Prior Art] In recent years, with the high integration and high speed of LSI, the pattern line has been rapidly becoming finer. Since the beginning of 1994, the load pattern of SI 设置 has been set to 0. 1 8 //m line design should start mass production in 2 〇〇 1 year, but actually 2 years earlier and 1 9 9 Mass production has started in 9 years. 0 · 1 8 // m design system starts with A r F etch printing, and is extended by lithography printing, and has been reviewed until now. J 5 # m, even arrived at 硏 〇 · 1 3 μ ιώ The mass production problem of K r F etching printing. Therefore, with the maturity of K r F etching printing, the miniaturization of the line has been accelerated. In recent years, the issue of reticle fabrication technology has been gradually discussed. The g-line era is a reduction in the projection exposure apparatus, which has a reduction ratio of 1 / 5 , but recently the wafer size has been enlarged and the large diameter of the projection lens has made the cycle 1 / 4 magnification. Therefore, not only is the line width reduced due to the microfabrication, but also the line width is reduced due to the change in magnification, which is a great problem in the reticle manufacturing technology. The exposure apparatus for mask production has been changed from an exposure apparatus using a laser beam to an exposure apparatus using an electron beam (E B ) in order to increase the accuracy of the line width. Among them, E B's electron gun can reach the paper speed J1 speed with the Chinese National Rate (CNS) grid (2iGX 297 mm) after raising the accelerating voltage (please read the back note before filling in this page)

-4 - A7 B7 Economy 郜 Smart Closing Bureau Employees' Consumption Cooperatives Printed Purple 1253543 V. Invention Description (2) The degree of miniaturization has changed from 10 k eV to 30 k eV, and 5 〇ke V has Recently formed a mainstream position. However, as the acceleration voltage increases, there is a problem that the photoresist is low-sensitivity. When the acceleration voltage is increased, the influence of the previous scattering in the photoresist film is reduced. Therefore, if the electron drawing energy can be controlled, the resolution or the size controllability can be improved, but since the electron system directly passes through the inside of the photoresist film, The sensitivity of the first resistance will decrease. The reticle exposure machine is exposed in a linear exposure mode. Therefore, the decrease in the sensitivity of the light resistance causes a decrease in productivity, which is a poor condition. The need for high sensitivity has gradually been reviewed to enhance chemically positive photoresist materials. However, the vacuum placed after exposure causes a change in sensitivity, or a problem such as a curled shape on the Cr substrate when the positive resist is applied. After exposure for a long time, when it is left in a vacuum for a long time, the acid generated by the exposure evaporates, and when it is not subjected to the dissociation reaction, evaporation will cause a low sensitivity. Even if P E B is carried out in dry air, nitrogen or argon, heating without dissociation reaction causes acid evaporation and low sensitivity. The edge of the substrate is curled. In the K r F etching, the problem should be the same as that caused by an alkaline substrate such as τ 1 N. To reduce the edge curl, the acetal can be used to be lower than the dissociation reaction. The substituent of the activated energy will have a better effect. However, by using the photoresist of the acetal substituent, it is noticeable that the sensitivity is gradually lowered after the exposure and the vacuum is placed. In the presence of water, the dissociation reaction by acid catalyst is an irreversible reaction, while the dissociation reaction in the anhydrous state is applicable to China National Standard (CNS) A4*l (2)0X29. *?mm) (Please read the notes on the back and fill out this page)

1253543 A? ____ B7 V. INSTRUCTIONS (3) Reversible reactions, and because of the extremely fast rate of the reverse reaction, the rate of dissociation reaction is very slow. (Please read the precautions on the back and fill out this page.) A method to prevent irreversible reaction of acetal in the absence of moisture, for example, adding a high-boiling alcohol. This method is as disclosed in the Japanese Unexamined Patent Publication No. Hei 1 1 1 1 1 1 1 3 . The high boiling point alcohol, after preheating or remaining in the vacuum film, will have the same effect as water and cause an irreversible dissociation reaction. However, the addition of alcohol causes an irreversible reaction in the dissociation reaction in the vacuum, so that high sensitivity is formed by the progress of the dissociation reaction in the vacuum. However, it is difficult to increase the stability in vacuum by the combination of acetal and alcohol-based additives. The present invention, that is, the event in the above case, provides an enhanced chemical positive resist for electron beam or soft X-ray exposure in which the sensitivity is minimally changed in the vacuum discharge after exposure, and the curl on the Cr substrate is small. The material is for the purpose of the invention. [Contents of the Invention and Embodiments of the Invention] The Ministry of Economic Affairs, the Intellectual Property Office, and the Employees' Fee Cooperatives Printed The present invention has been completed in order to achieve the above object. The dissociation reaction formula of the acetal substituent in the absence of moisture is as follows (a) - 1 , and the reaction formula in the presence of water is as follows (曰-2). Even in electron lines or soft X-rays. Under exposure, the same phenomenon occurs when the post-exposure (PEB) is carried out in a dry air, nitrogen argon or helium atmosphere with a humidity of less than 20%. This paper scales with the Chinese National Standard (CNS). A4 Washing (2丨〇X 297 公羡) -6 - 1253543 Α7Β7 Ministry of Economic Affairs Intellectual Property Bureau Staff Expense Cooperatives Printed Purple Five, Inventions (4)

Further, the hydroxy group of the carboxylic acid or phenol is substituted with a 3-stage hydrocarbon group, and the dissociation reaction is carried out even in the absence of moisture. This reaction formula is as shown in the formula (b). As a result of the experiment, it is found that in the tertiary hydrocarbon substituent, the substance having a higher dissociation reactivity is subjected to a dissociation reaction by being placed under vacuum after exposure. In this case, the acetal group exhibits a high degree of entanglement in contrast to the acetal. Therefore, when the acetal group is combined with the tertiary hydrocarbon group having a high dissociation reactivity, the mutual disadvantages can be complemented and the vacuum can be increased after exposure. Earthquake stability. Further, the third-stage hydrocarbon group having a higher reactivity is less likely to cause edge curling in the vicinity of the substrate, so that the combination of the acetal group can reduce the occurrence of the roll on the substrate.

At this time, the dissociation reactivity of the tertiary hydrocarbon gene is high, so it is necessary to reduce the activation energy of the dissociation, and the substituent having a higher activation energy is placed under vacuum, and the stability of the sensitivity is higher because the dissociation reaction is not performed, but Will cause a curling situation. If you want to reduce the curling condition and use it in combination with the acetal group, you can use the Chinese National Standard (CNS) Α4 Washing (210Χ 297 mm) for the paper scale (please fill in the back of this page) 1253543 B7 V. Description of the invention (5 acetal group can not prevent low-sensitivity bismuth 〇 结果 〇 ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ ϊ 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若The performance of the above is not satisfied. 〇In order to increase the dissociation reactivity of ter ΐ butyl to enhance the electron density of the third-order hydrocarbon, especially to form the ring to dissociate • the method of producing olefins is better. For example, 9 is more tert a compound having a higher reactivity and having a cyclic structure, a compound having a cyclic structure, or a compound having an aryl group, has high reactivity. Thus, the present invention provides a plant. There are the following reinforced chemical resistive materials. Please refer to item 1: - Reinforced chemical positive resistive materials for electron beam or soft X-ray exposure. They contain one or more kinds of carboxyl or phenolic hydroxyl groups. A reinforced chemical positive-type photoresist material which is a base polymer 5 which is soluble in an aqueous alkali solution and at least a part of a hydrogen atom of a carboxyl group or a non-phenolic hydroxyl group is an alkali-insoluble or poorly soluble resin which is introduced into an acid labile group. 5 and the above resin is a small amount of two kinds of acid-unstable cadaveric bases. One of the acid-labile groups is the acetal or ketal shown by the following formula (1) 1 N ( 1 ) 2 or ( 1 ) 3 The other part of the Kiji Department is: the acid-labile group is a hydrocarbyl group of the following formula: 2) or (2) a 2 ΤΓ ν 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智 智3 Production Bureau Substituent of g-hydrocarbyl group • '工消f > ύν 十 C-OR3 (Λ V1 for R2 / Co-printed paper scale speed Chinese national standard (CMS) A4 this grid (2) 0X297 mm) .8 · 1253543 A7 B7 Ministry of Economic Affairs Zhi Chu Firing Bureau employees Xiaohuang Cooperative Printing 5, invention description (6) (where R1 ' R2 is a hydrogen atom or a linear or branched chain of 1 to 20 carbon or a cyclic alkyl group which may contain a hetero atom such as oxygen, sulfur, nitrogen, fluorine, etc., R] and R2 'R] and R3 'R2 and R3 may each bond to form a ring 'R3 is a linear chain having a carbon number of 1 to 2 0 a branched, branched or cyclic alkyl group, or an aryl or aralkyl group having a carbon number of 6 to 20, which may contain a hetero atom such as oxygen, sulfur, nitrogen or fluorine)

R 19

R 19 R20 heart 0 (1>·2

R 19

R 19 —C_〇—R21- B—A—+B+R21 — O—^C Seven R20 R2〇a-like, branched cycloalkyl; affinity, number 1 to ring, atomic C '3 is a scorpion in the formula, RR 2 b , 5 0 such a part (servant 3, R19, R2G is a hydrogen atom or a linear or cyclic alkyl group having 1 to 8 carbon atoms, R19 and R2C) can be bonded Forming a ring, 彤19, R20 are a straight or scorpion-like extension of carbon number 1 to 8 and a linear, branched or cyclic extension of carbon number 1 to 1 c is 0 or 1 to 1 〇 An integer; A is an aliphatic or alicyclic saturated hydrocarbon group of a + 1 valent carbon, an aromatic hydrocarbon group or a hetero group may have a hetero atom incorporated therein, or a hydrogen bond bonded to such a carbon atom may be a hydroxyl group or a carboxyl group. , carbonyl or fluorine atom substitution; B 〇 one, one NHC 〇 one or one NHC0NH — the integer of 1 to 7 ra- R6) (2)-1 Shi Jin / ίίΙ) in the middle of trouble, u (read Read the notes on the back and fill out this page.

C 3 i- i [ ! w V -

* y X 9 1253543 Λ7 B7 Ministry of Economic Affairs Zhizhi Property Bureau employee consumption cooperatives printed ^ 5, invention description (7)

, 〇 R7 11 I. iCH2)d a C-〇-〇RS (3)-1 (wherein R4 to R9 are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a carbon number of 6 to 2 An aryl group of 0, at least one of R4, R5, and R6 and at least one of R7, R8, and R9 are a cyclic alkyl group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. The base may contain a hetero atom such as oxygen, sulfur or nitrogen 'fluorine, or R4, R5, R6 and R7, R8 and R9 may be bonded to each other to form a ring having a carbon number of 5 to 30. These rings may contain oxygen and sulfur. a hetero atom such as nitrogen or fluorine; further, the carbon number of R4, R5, and R6 is the total, and the carbon numbers of R 7 ' R δ and R 9 are each a total of 6 to 30; d is an integer of 0 to 4)

〇(2)·2 (3)>2 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R1C), R14 Any one of a cyclic alkyl group having 5 to 20 carbon atoms or an aryl group having 6 to 2 carbon atoms may contain an integer of 1 to 3 of a hetero atom such as oxygen, sulfur, nitrogen or fluorine. Application 2: e is (Read the first note on the back and fill out this page)

This paper scales the speed of China's ffi family standard (C^JS) A4 said grid (2) OX 297 gong t). 1〇. 1253543 A7 —__________B7__ — V. Invention description (8) ~ ® m strand or soft X A reinforced chemical positive-type photoresist material for line exposure, which comprises a base polymer which has a carboxyl group or a phenolic hydroxyl group as a soluble base polymer and which is at least a part of a hydrogen atom of the carboxyl group or a phenolic hydroxyl group. An alkali-insoluble or poorly soluble resin containing an acid-labile group substituted with a condensed or ketal group of the formula (; L )-1, (1)-2 or (1)-3, and having a carboxyl group Or the phenolic hydroxyl group is a soluble base polymer in the aqueous base solution and at least a part of the hydrogen atom of the carboxyl group or the phenolic hydroxyl group is represented by the above formula (2)-i or (2)-2. A tertiary hydrocarbon group or an alkali-insoluble or poorly soluble resin containing an acid labile group substituted with a substituent of the tertiary hydrocarbon group represented by the above formula (3)-i or (3)-2. Application 3 · An electron beam or soft X-ray exposure week-enhanced chemical positive-type light, which is a base polymer containing a carboxyl group or a phenolic hydroxyl group to an aqueous alkali solution, and a hydrogen atom of the carboxyl group or a phenolic hydroxyl group An acid labile group substituted by the above formula (1)-1, (1)-2 or (1)-3 acetal or ketal group, and at least a part of the remaining hydrogen is as described above (2) - 1 or (2) - 3 hydrocarbon group or an alkali-insoluble or resin containing an acid labile group substituted by a substituent of the hydrocarbon group of the formula (3)-1 or (3)-2. Application 4: For the photoresist material of the first, second or third patent application, there is an organic solvent and an acid generator. This paper is used in China National Rate (CNS) A4 (2丨〇 X 29*7 mm). (Read the first note on the back and fill out this page)

The soluble part of the 'II resistive material, the 2 shown in the atom indicates the poor solubility of the third grade. The 尙 contains the Ministry of Economic Affairs, the Intellectual Property Bureau, the employee's fee, the cooperative, the Indian purple 1253543 at _______B7, the invention description (9) The photoresist material according to any one of claims 1 to 4, which contains a basic compound. (Please read the precautions on the back and then fill out this page.) Item 6: The photoresist material according to any one of claims 1-5, which contains a dissolution inhibitor. Hereinafter, the present invention will be described in more detail. The reinforced chemical positive resist material of the present invention is used for electron beam or soft X-ray exposure, which comprises one or more kinds of base polymerizations which are soluble in an aqueous alkali solution containing a carboxyl group or a phenolic hydroxyl group. And at least a portion of the hydrogen atom of the residue or the benzene-based radical is a reinforced chemical positive photoresist material which is introduced into an alkali-insoluble or poorly soluble resin of an acid labile group, and the upper 5 sap Ss It is at least two kinds of acid-labile groups, one of which is substituted by the formula (1)-1, (1)-2 or (;[)-3, which is substituted by a fluorene or ketal group. The obtained first acid labile group, and the other acid labile group is a tertiary hydrocarbon group represented by the following formula (2)-1, (2)-2, (3)-1 or (3)-2 The second acid-labile group substituted by the substituent; the Ministry of Economic Affairs has printed seven orders R3) (1)-1 R2 (in the formula, R1 and R2 are hydrogen atoms or carbon number 1 to 2 直 linear, branched or cyclic alkyl 'which may contain heteroatoms such as oxygen, sulfur, nitrogen, fluorine, etc., R] and R2, and R3, & 2 and] [^3 may be bonded to each other Forming a ring 'R3 is a linear, branched or cyclic alkyl group of 1 to 20, or an aryl or aralkyl group having a carbon number of 6 to 20, which may contain oxygen, sulfur, nitrogen, or the paper. China® Home Snap (CNS) Grid (2丨0X 297 mm) ' 1253543 Α7 _Β7 V. Invention Note 0〇) Heteroatoms such as fluorine) R + CHlR20 21 R of Af o-VR2 R, R1eb

V 0 1 21 R + B A-+ I B I 21 R

RIC 20 c^Rθ I 1 -2

Lc -o 2 - R *3 (wherein R19 and R2D are a gas atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and R39 and R2 may be bonded to form a ring to form a ring. When R19 and R20 are a linear or branched alkyl group having 1 to 8 carbon atoms; R21 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and b and c are An integer of 0 or 1 to 10; A is an aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and may have a hetero atom in the group. Or a part of a hydrogen atom bonded to such a carbon atom may be substituted by a hydroxy 'carboxy' carbonyl or a fluorine atom; B is a C 〇 〇 , an NHCO — 〇 1 or a NHCONH — , a is 1 To the integer of 7) ra (2)·1 (please read the notes on the back and fill out this page)

Printed by the Huangchu Cooperative of the staff of the Ministry of Economic Affairs

0 R7, -(CH2)d-OOC^RS (3)-1 (wherein R4 to R9 are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a carbon number of 6 To the aryl group of 20, at least one of R4, R5, and R6 and at least one of R 7 and R Β ' R 9 are carbon number 5. The paper speed is measured by China National Standard (CNS) Α4λ grid (2 〇X297嫠) .13 - 1253543 Λ7 B7 V. Inventive Note (Ή) to 2 〇 cyclic alkyl or 6 to 20 aryl, these may contain oxygen, sulfur, nitrogen, a hetero atom such as fluorine, or R4 'R5, R6 and R7, R8, R9 may be bonded to each other to form a ring having a carbon number of 5 to 30, and these groups may contain a hetero atom such as oxygen, sulfur 'nitrogen, fluorine or the like; R4 'R5, R6 carbon number total, R7, R8, R9 carbon number total 6 to 3 〇 stomach; d is 〇 to 4 integer)

〇, (Please read the note on the back and fill out this page) (2)-2 (3>2 (in the formula, R].' R14 is a straight, braided or ring with a carbon number of 1 to 20. An alkyl group, or an aryl group having a carbon number of 6 to 20, R 10,

Any one of Rl4 is a cyclic alkyl group having 5 to 20 carbon atoms or an aryl group having 6 to 2 carbon atoms, and these groups may contain hetero atoms such as oxygen, sulfur, nitrogen, fluorine, etc., and e is 1 to 3 Integer). Wisdom of the Ministry of Economic Affairs-Industry of the Department of Labor and Welfare Cooperatives, Ink, in this case, in the photoresist material of the present invention, the alkali-insoluble or poorly soluble resin is used as the base resin, so it has the first acid-stabilized group. a blend of an alkali-insoluble or poorly soluble resin and an alkali-insoluble or poorly soluble resin having a second acid labile group, that is, in the photoresist material, the base resin is composed of a base having a carboxyl group or a phenolic hydroxyl group. The aqueous solution is a soluble base polymer, and at least a part of the hydrogen atom of the carboxyl group or the phenolic hydroxyl group is subjected to the above formula (1)-1, (1)-2 or (1) China National Standard (CMS) Α 4 Washing (210X 297 mm) .14 - Ministry of Economic Affairs Zhichu 対 员工 Employees' Consumption Cooperatives Printing and Burning 1253543 -- V. Invention Description (η )

Η Η (wherein R31 and R32 are a hydrogen atom' or a direct bond, a branched or cyclic alkyl group or a fluorinated alkyl group having a carbon number of 1 to 1 Q; and R33 is a linear chain having a carbon number of 1 to 1 Å. a branched or cyclic alkyl group which may also contain an oxygen atom in the form of a hydroxyl 'ethyl hydrazide group, a vine group or an ether group, X is from 1 to 4, y is an integer from 1 to 3, and q is 〇 Or 1) Also, the basic polymer soluble in the alkali aqueous solution, in addition to the above list, can also be combined with acrylic acid derivatives, methacrylic acid derivatives, raw spinach derivatives, anhydrous maleic acid, and maleic acid. A copolymer of an imine, an acrylonitrile 'ethyl acetate, an ethyl ketone alcohol, a tetrafluoroethylene, or the like may be obtained. Further, the molecular weight of the base polymer is preferably in the range of 2,000 to 1 Torr and 〇0 于 in the weight average molecular weight. Further, the base polymer which is soluble in the aqueous alkali solution may be a dendritic polymer having a repeating unit represented by the following formulas (I) and (I I ) or a net-branched polymer. R42

(H〇)z (R40)m This paper ruler Jl speed is used in China National Standard (CNS) (210X297 public)-16 ^ (please read the note on the back and fill out this page)

1253543 V. INSTRUCTIONS (14) A7 B7 Ministry of Economic Affairs, Intellectual Property Office, 贽合ΐ, R19 R1 丄20 (II) (wherein only 4[) is a hydrogen atom, a linear number of carbons 1 to 20, a branched or cyclic alkyl group, or an aryl group having 6 to 20 carbon atoms; R42 is a hydrogen atom, or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and R43 is a carbon number a linear, branched or cyclic alkyl group of 1 to 20, or an extended aryl group having a carbon number of 6 to 20, which may also contain an ether bond or an ester bond; 2 is 1 to 5, m is an integer of 1 to 5, z + mS5) The alkali-insoluble or poorly soluble resin used in the present invention is at least a part of a hydrogen atom of a carboxyl group or a phenolic hydroxyl group of an alkali-soluble resin as described above. The above is substituted with the first acid labile group or the second acid labile group. Here, the first acid-labile group is represented by the following formula (1)-1 to (1)-3. R1 4-0 - R3, (wherein, R1 and R2 are a hydrogen atom or a straight-chain branched or cyclical base having a carbon number of 1 to 2 Å, which may also contain oxygen, sulfur, nitrogen, fluorine, etc. a hetero atom, R] and R2 'R] and R3, R2 and R3 may each bond to form a ring; R3 is a linear, branched or cyclic fluorenyl group having a carbon number of 1 to 20, or a carbon number of 6 An aryl or aralkyl group of up to 20, which may contain heteroatoms such as oxygen, sulfur, nitrogen, fluorine, etc.)

R The paper size is applicable to China K*: 梂准(CMS) 格U丨0X297 mm) .^ ^ η Read the back first 5 i Livestock Fill in this page Economic Department Zhi.% Xie Production Bureau Staff Consumer Cooperative Print ^

1253543 Α7 Β7 V. Description of invention (15) R10 r1b —f-O-R21- B-A-fB+R21 −. 7-〇7-R20 p2〇8 (wherein R]9 and R2D are a hydrogen atom or a linear 'branched or cyclic alkyl group having 1 to 8 carbon atoms. Further, R]9 and R20 may be bonded. The ring forms a ring, and when the ring is formed, R19 and R2 are straight or branched alkyl groups having a carbon number of 1 to 8. R21 is a linear, branched or cyclic stretch of carbon 1 to 1 Torr. The alkyl group 'b, c is an integer of 0 or 1 to 1 ;; an aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group having 3 to 1 valence, such a group a hetero atom may be interposed, or a part of a hydrogen atom bonded to a carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom; B is a C〇-〇, an NHC〇-〇- or a NHCONH — , 3 is an integer from 1 to 7) In the formula (1)-1, R1, R2 and the alkyl group thereof are specifically, for example, methyl, ethyl, propyl, isopropyl 'butyl' sec-butyl' Ter ΐ —butyl 'cyclopentyl ' cyclohexyl ' 2 -ethylhexyl, η -octyl, etc.; part of the hydrogen atom in such alkyl group may be hydroxy, alkoxy 'carbonyl, amine, alkylamine The substituent may be substituted, and the specific one is, for example, a substituted alkyl group as described below. —(CH2)4OH —(CH2)2〇(CH2)3CH3 —ch2-^—,—ch2oh

One (CH2)20(CH2)20H—(CH2)60H R and R, R and & 3, ruler 2 and 1^3 can form a ring, forming a ring-shaped paper scale applicable to China National Standard (CNS) Α4*υΓΓΓ ^Γ297公I)~- 18 · ' (Please read the back of the note before you fill out this page)

1253543 a7 B7 V. Inventive Note (16), each of R), R2 and R3 is a linear or branched alkyl group having 1 to 18 carbon atoms, preferably 1 to 1 Å. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an isobutyl group, a cyclohexyl group, a cyclopentyl group and the like. Further, specific examples of the aryl group of R3 include a phenyl group, a methylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group and the like. Specific acetal groups are as shown in the following formula (6) - 1 to (6) - 29. (Please read the notes on the back and fill out this page)

Printed by the Ministry of Economic Affairs, Zhichu Property Bureau, Staff and Cooperatives

3 Η H clCH n3 H2 -CH-10 ?(6)

N3 c 1 2 H (cT H3-0 CH丨CH 3 V1 (6

Hs c I n2 CH ό H3H2H- clclCH

ο Η3Η2Η-CI(ClCH H3 ch ^1 (6) 2 VI.

^ •CH 2· H (co- H3H2H-cICIC

H3 c IH (cT ho H3H2H-C1 (C1CH 5 ΑΊ valence - CHj - 〇 CH CH3 · 二 CH) - 〇-CH. One CH3 - 0^-0(0^2)2 - CH: (6)-1 (6)·2 (6)·3 ch3 ch3 ,CH2-〇-(CH2)3-CH3 a ch2 point CH-CH3 a ch2-〇-c a ch3 I ch3 (6H (6)-5 (6)- 6 ch3 ch3 ch3 i ch2 - c!h - 〇-ch3 (CH2)2 -CH-0-CH3 one CH-〇CH3 (6)-7 (6)-8 (6)-9 This paper size applies to China Sample Standard (CNS) A4*t Grid U丨〇X 29*7 嫠) [253543 A7 B7 V. Invention Description (17 ch3 ch3 ch3 — CH—〇—一CH 一〇〈〉—CO-CHj (6) -16 (6)-17 ch3 (6)-18 CH3 丨~ —C—O-CHj-CH-a I ch3 (6)-19

(6)*23 (6)-20 (6>21 (6)-22 CH3 —CH-〇~<^ (6)-24 (6)-25 (6)-26 〇 ch3 a CH—〇

(6)·27

(6)-28 (6)·29 Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs (Read the first note on the back and fill out this page)

This paper scale is applicable to China's national standard (〇^) six 4*1 grid 〇丨0><297 thin) 1253543 A7 B7 V. Invention description (18 Second, formula (1) 2 (1) 3

R

R's yard, R]

R

The alkylene group of R is as exemplified above. Further, the specific example of 1 A is as follows. The cross-linking group (1)-2, (1)-3 is a cross-linking group formed by an enolate compound or a halogenated alkyl ether compound described later, and is represented by the above formula (1). It is known that after 2 '(1)-3, it is not limited to the two-valent, but also the 3- to 8-valent linkage, and the trivalent cross-linking group is as shown below. For example, the intersection of two prices r19 R 4 Ο-A - 〇{ R21_ 〇} 19

R 20

R , 20 R19 R —j-〇~R21-B-A - B+R21 -. Yun 19

R, 20

R , 20 19 R1-

21 R A—-—ο—

rR20 C^ - R2R CH Ministry of Economic Affairs. % Property Bureau employees> «Loan cooperatives printing ^ 9 R1li o-

B- 21L R J\T21 AIBIR' Ο

1S20 RldR Λ (Please read the back of the M first and then fill out this page)

This paper is used in China's national standard (CMS) A4*t grid U]〇X297 mm) · 21 - 1253543 a7 r---~_____B7___ V. Invention description (19) where 'the upper cross-linking base In the description of A, the a + _1 valence of a, the specific hydrocarbon group is preferably a carbon number of 1 to 疋 1 to 40 mixed with hydrazine, NH, N(CH3), $, S〇2, etc. The unsubstituted or substituted radical of the atom, preferably substituted by a hydroxyl group, a carboxyl group, a decylamino group or a fluorine atom, is preferably a carbon number of 6 to 5 Å, especially a 6 to 40 aryl group and such alkylene a base of a aryl group bonded to a aryl group, a 3- to 8-valent group obtained by dissociating a hydrogen atom bonded to a carbon atom of each group, and the like, and a heterocyclic group such as a+1, such as a heterocyclic group The base obtained by hydroxy bonding and the like. The Ministry of Economic Affairs, the Intellectual Property Office staff, the goods and cooperatives, the printing and burning cooperatives (please read the notes on the back and fill out this page)

This paper scale is applicable to China National Sample Car (CMS) A4 Grid (2! 0X297). 22 - 1253543 A7 B7 V. Invention Description (2〇) -CH2CH2- , *(CH2)3**, -CH- CH2- > -(CH2)4·CH, _CHrCH- , -CHCH2CHr C2H5 ch3 -(CH2)5- 2" H2--CHH2-C-heart-C 3 Η C 2~ Η29Η2 C ——C--C Η2- 3CH Η C H3-CHH3 C—ό—c H2-9

-{ΟΗ2〇Η2〇)3 CH2CH2-, {CH2CH2O)"Ά〇_ _CΗ2·CΗ even)4 斗〇-(CH2) 士5-10 -CH2^CH2-0-CH2-CH2^ , -CH2~ CH2-CH2-O-CH2-CΗ- Employees of the Ministry of Economic Affairs, the Ministry of Economic Affairs, the Consumers Association, and the Consumers’ Association, ^CH-CH2-〇-CH-CH2-, -CH-CHrO-CH-CHrO-CH-CHr CH3 ch3 CH, k CH, (Read first «Read the back of the note and fill out this page again)

This paper is applicable to China National Sample Vehicle (CNS) A4 This grid (2丨0X297 mm) -23 · [253543 A7 B7 V. Inventions (21) CH2OHI • CH2 Heart CHr , ch2oh CH2OHI -CH 2~C-CH2&quot ;I CHr

r Η丄H2 c1-C-c *2 H -C 2 ^c HIC H 〇1c

—H •2 Hc H 〇1cjH H 〇1c丨H H —o Π2c

C—H H1c丨

Ho-c

—H c1H 2 Hc

N2 -C

Hie — I —C—H

2" Hc HI 〇1cjH I lie 1H Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printing ffc One paper

Ns c prospective home thank you (read the first note on the back and fill out this page)

4 A ΐ 一公 7 9 2 X ο 24 1253543 λ7 ______Β7 V. Description of invention (22) Printed by the Ministry of Economic Affairs Zhichu Property Bureau staff levy cooperative

(Please read the notes on the back and fill out this page)

1253543 A7 B7

V. Description of the invention (23) CHU

CH 3

Printed by the Ministry of Economic Affairs Zhizhi Property Bureau staff levy cooperative

This paper scale is speeded up by China National Standard (CNS) (2〗 0X297) (Please read the notes on the back and fill out this page)

1253543 Ministry of Economic Affairs Zhichu Tree Bureau employee consumption cooperative printed A7 B7 V. Description of invention (24) Also, using these C-〇-C-based crosslinking groups to produce high intermolecular and / or intramolecular crosslinking In the case of a molecular compound, a non-crosslinked polymer compound to be used is obtained by reacting a olefinic ether under an acid catalyst under a general method. Further, when the other acid labile group is decomposed under the acid catalyst condition, it is required to react with hydrochloric acid or the like to form a halogenated alkyl ether, and then react with the polymer compound under basic conditions according to a general method. And the object to be obtained is, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, 1,3-propylene glycol divinyl ether. 1,3,butanediol divinyl ether, 1,4-butanediol divinyl ether, neopentyl glycol divinyl fluorene, trimethyl cellulose propane trivinyl ether, trimethyl cellulose Ethane trivinyl ether, hexanediol divinyl ether, 1,4-divinyloxymethylcyclohexane, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, Pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol divinyl vinyl ether 'triethylene glycol divinyl vinyl ether, trimethyl cellulose propane triethylene ethylene Ether, trimethyl cellulose propane divinyl vinyl ether, Pentaerythritol divinyl vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetravinyl vinyl ether, and compounds represented by the following formulas (I-1) to (I31). This paper scales with China® Family Rate (CNS) (2) 0X297 cm) · 27 · (Please read the back note and fill out this page)

1253543 A7 B7 V. DESCRIPTION OF THE INVENTION (25 CH2=:CH-OCH2CH2〇—^—OCH2CH2〇-CH:=CH2 (Μ) CH2=CH-〇CH2CH2〇\ /och2ch2o-ch=ch2

(Ι·2) ch2=ch-och2ch2o b- (Notes on the back of the poem read the first page) 0CH2CH20-CH=CH2 (卜3) ch2=ch-och2ch2o

0CH2CH20-CH=CH2 (Μ)

Ch2=ch-och2ch2o —^( —och2ch2o-ch=ch2 (b 5) The Ministry of Economic Affairs Zhichu Property Bureau employees Xiaohuang Cooperatives Printed in purple paper, the standard speed of China National Standard (CNS) A4 Wash (210X 297 PCT) -28 1253543 (Please read the note on the back and fill in this page)

A7 B7 Ministry of Economic Affairs, Ministry of Economic Affairs, Production Bureau, Consumers, Cooperatives, Printing 5, Inventions (26) ^^2=^H-OCH2CH2〇—C~JL 〇OCH2CH20-CH=CH2 (i-6) ch2=ch-〇ch2ch2o —1 jl s \〇CH2CH20-CH=CH2 (1-7) ch2=ch^och2ch2o—n^〇ch2ch2〇.ch=ch2 (l7) ch3 /QCH2CH2〇-CH=CH2 I ch2=ch-och2〇 H2〇—(~y (4)\〇CH2CH2〇-CH=CH2 ch3 j ° CH2=CH-QCH2CH2C)— ch3 j (M〇) This paper scale is sent to China National Standard (CNS) A4 Wash (210X 297) PCT) -29 1253543 A7 B7 V. Description of invention (27) ch2=ch-〇ch2ch2o

Och2ch2o-ch=ch2 (卜11) ch2=ch-och2ch2o

Och2ch2o-ch=ch2 (M2) ch2=ch-o-ch2o

Ch3 C 〇CH20-CH=CH2 (M3)

(M4) Printed by the Intellectual Property Office of the Ministry of Economic Affairs

NH 5) (Read the first note on the back and fill out this page)

This paper scale applies to China National Standard (CNS>A4 this grid<21 OX 297 mm) -30 1253543 Λ7 ____ _B7 V. Invention description (28) CH2=CH-0

O-ch=ch2 (M6) CH〇=CH-0

0-CH=CH2 (ΙΊ7) CH2=CH-0—〇-CH=CH: 0-18) ch2=ch-o 〇.CH=CH2 (M9) ch2=ch-o

O-ch=ch2 (U20) 〇 The Ministry of Economic Affairs, the Intellectual Property Office employee's levy cooperative printing (please read the back of the M first and then fill out this page)

This paper is applicable to China National Standard (CNS) A4 Washing (2]ΟΧ29*7 Gongqing) 1253543 A7 ^ _B7 V. Invention Description (29) ch9=ch-o

(卜 21) ch2=ch-o

〇^CH=CH2 (1-22) (Please read the note on the back and fill out this page) o-ch=ch2,*!! Economics and wisdom are printed on the employees of the production bureau. ch2=ch-o

(1-23) (1-24) $ This paper scales the speed of China's household sample rate (CNS) A4*l (2) 297 297 mm) -32 · 1253543 A7 B7 V. Invention description (30 ch2= Ch-o

〇-ch=ch2 (卜 25) 0-CH=CH〇 ch2=ch-o

(1-26) 0-CH=CH2 Printed by the Ministry of Economic Affairs

(卜 27) This paper scale is stated in China National Standard (CNS) (210X29*7 public) (please read the following on the back of the page)

-33 - A7

Ministry of Economic Affairs, Zhisheng Property Bureau, Staff Consumption Cooperative, Printing Disaster 1253543 :_B7 V. Invention Description (31)

(Please read the notes on the back and fill out this page) ch2=ch-o ch2=ch-〇

(Bu 31) Further, for example, terephthalic acid divinyl vinyl ether, phthalic acid divinyl vinyl ether 'isophthalic acid divinyl vinyl ether, phthalic acid dipropylene vinyl ether 'p-benzoic acid Acid dipropylene vinyl ether, isophthalic acid dipropylene vinyl ether, maleic acid divinyl vinyl ether, fumaric acid divinyl vinyl ether, itaconic acid divinyl vinyl ether, etc., or the following formula (I 1 to 1) to (II-11), but not limited to the above compounds.

This paper is suitable for China National Standard (CNS) Α4玑 (210X 297 mm) -34 - 1253543 A7 B7 V. Invention Description (32) ch2:choch2ch2〇〇cnh-nhc〇och2ch2〇ch=ch2 (IM ) CH2=CH0CH2CH20〇CNH\ /NHCOOCH2CH2OCH=CH2 (Π-2)

Chb=CHOCH2CH2〇〇CNH—^yHf^y—NHC〇〇CH2CH2〇CH:CH2 (H-3) ch2=ch〇ch2ch2nhcnh 〇

NHCNHCH2CH2〇CH=CH2 II 〇 (1M) (Please read the notes on the back and fill out this page)

CH 3 CH2=CHOCH2CH2〇〇CNH—--nhcooch2ch2och=ch2 ch3 (1 bu 5) cf3 Ministry of Economic Affairs Zhizhi Property Bureau employee loan cooperative cooperative printing ch2=:choch2CH2〇〇cnh one

CF, •nhc〇och2ch2〇ch=ch2 (Π-6) - 35- This paper is measured at the speed of China National Rate (CNS) A4 (2) 0X29*? mm) 1253543 A7 B7 V. Description of invention ( 33 ch9=choch2ch2oocnh

NHC00CH2CH20CH=CH2 (11-7) CH, CH: :ch〇ch2ch2nhcnh^^~|~{3·—NHCjjNHCH2CH2〇CH=CH: d CH3 ο (11-8) ch3 CH2=CHOCH2〇〇CNH —^^NHCOOCH2OCH =CH2 CH, CH, (Please read the notes on the back and fill out this page)

CH 2' CHOCH2NHCNH -NHCjjNHCH2〇CH=CH2

CH 3 (1M0)

CH :choch2chp〇cnh-^Q~ch2-^-nhcooch2ch2och=ch: (IM1) 1 Ministry of Economic Affairs Zhizhi 3⁄4 Production Bureau Staff Credit Cooperatives India Purple (1) 1 2' (1) - 3 For example, the compound shown in the following formula (7) - 1 to (7) - 8 is used in the Chinese national standard (CNS) A4. This is a grid of u) 0 X 29*7 mm 〉 -36 - 1253543 A7 B7 V. INSTRUCTIONS (34 CH3 ?H3 I 1 -CH-O-CH2CH2OOH"

Ch3 ch3 -ch-o-ch2ch2ch2ch2-o-ch^ ch3 CH3 -ch-o-ch2ch2och2ch2och2ch2-o-ch- ch3 ch3 CH3 -CH-0-CH2CH2〇*x ch3

〇· och2ch2-o-ch- (7)-1 (7)-2 (7)-3 (7)·4 (7)-5 (7)-6 (Please read the notes on the back and fill in the form) Page) Ministry of Economic Affairs Zhi Chu Firing Bureau staff lending cooperatives India purple

(7) - 7 (7)-8

This paper and scale speed use China National Brake (CNS) A4 This grid (2; 0X 297 mm) • 37 - 1253543 A7 B7 V. Description of invention (35 Further, the second acid unstable group, for example, the following formula (2 -1 - 1 2 2 3) -2 Compound ra (2)-1 〇R/ II I 9 -(CH2)cj~C-〇-C-R9, u R8 (3)-1 (wherein R 4 to R 9 are a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and at least one of R 4 , R 5 and R 6. 7. At least one of R 8 and R 9 is a cyclic alkyl group having 5 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and these groups may contain oxygen, sulfur, nitrogen, fluorine, and the like. Atom, or R4; R5, R6 and R7, R8, R9 may be bonded to each other to form a ring having a carbon number of 5 to 30, and such rings may contain a hetero atom such as oxygen 'sulfur, nitrogen, fluorine, etc.; and 'R 4, R5' R6 carbon number in total, R7 'R8, R9 carbon number totals 6 to 30 each; d is an integer from 0 to 4) Ministry of Economic Affairs. ^ Finance 1 Bureau employee consumption cooperative printing ^ R10

R10 " /R10 (2>2 (3)-2 R' (wherein R, D, R14 are a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a carbon number of 6 to 20 aryl, R)C), (please read the notes on the back and fill out this page)

This paper scales the speed of China's national standard · (CNS) grid (2丨0 X 297 mm) · 38 · 1253543 A7 B7 V. Description of invention (36) Any of R34 is a ring of carbon numbers 5 to 20 An alkyl group or an aryl group having 6 to 2 carbon atoms, and these groups may contain a hetero atom such as oxygen, sulfur, nitrogen or fluorine, and e is an integer of 1 to 3. In the formulae (2) - 1 and (3) - 1, the alkyl group and the aryl group of R4 to R9 are as exemplified above. The alkyl group of the formula (2) -1, (3) - 1 and the acid labile group substituted by the substituent of the class 3 hydrocarbon group, for example, the following formula (4) -1 to (4) - 2 7 The exemplified. , 10 R 10

R

R

(2 points)

R10 R1

12

R 10 (4)-5 (Please fill in the page on the back of W#)

,tT (4)·1

R

R R10 〇11

This paper and scale apply to China National Standard (CNS) A4*t grid < 2丨0 X 29*? mm) 1253543 A7 B7 Ministry of Economic Affairs Zhichu on the Bureau of Labor and Expenses Cooperatives Printed Purple Five, invention description (37

R1. \ hv) (4)-19 (4>20

(4)-21 R1 .(外 23 Ύ 0 R (4)-27 R 1〇 R 11 〇,

-.10

R 10 R Ή

secret. : (4)-26 wherein R1^ is a straight or branched, cyclic or alkyl group of the same or different carbon number of 1 to 8, or an aryl group having a carbon number of 6 to 20, R11, R13 is a hydrogen atom, or a straight, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R12 is an aryl group having 6 to 20 carbon atoms. In this case, the alkyl group of R 1 i R ] 3 and R 1 3 is, for example, the same as those enumerated above. Further, R 1 D, R 1 1 and R 1 3 may be doped with a hetero atom such as oxygen, nitrogen or sulfur, and specific examples thereof are as exemplified in the following formulas (5)-1 to (5)-7. (Please read the notes on the back of the gods and fill out this page)

This paper scale speed is used by China National Brake (CNS) A4*l grid UjOX: ^7 mm) -40- 1253543 Α7 •__Β7 V. Invention description (38)

—(CH2)4OH —(CH2)20(CH2)3CH3 — CH2 ~(^—CH2OH ! (5>1 (5)·2 (5).3

—fCH2)20(CH2)2〇H —(CH2)6〇H

(5H (5)-5 (5)-6 -CH-

(5)-7 Further, in the formula (2)-2, (3)-2, R 1 0 is the same as the above, and an alkylene group or an extended aryl group of R 1 4 is, for example, an alkyl group as exemplified above. The base is obtained by removing one hydrogen atom. Further, the acid labile group of the formula (2)-2 and (3)-2 is exemplified below. (Read the first note on the back and fill out this page}

〇 f 40+ is

Λ, 1Τ The alkali-insoluble or poorly soluble resin having an acid-labile group is as follows: The repeating unit represented by the following formula (8). For example, the Ministry of Economic Affairs, the Intellectual Property Bureau, the Employees' Consumption Cooperative, printed this paper scale, and the Chinese National Standard (CNS) Α4 Washing (2) 0X 297 mm) ^ ^ A7 B7 Ministry of Economic Affairs Smart Production Bureau Employees Consumption Cooperative Printed 1253543 V. Description of invention (39)

(8) Among them, R3. The above-mentioned acid labile group, the contents of R 31 and R32' R 3 3 are as described above. In this case, the group of R 3 1 and R 3 2 is, for example, exemplified above, and a fluorinated alkyl group such as a part or all of the hydrogen atoms of such an alkyl group is replaced by a fluorine atom. Further, the alkylene group of R 3 3 is, for example, the same as the previously exemplified one. k, n is an integer from 1 to 5, m is 0 or an integer from 1 to 4, 〇 is 0 or an integer from 1 to 3, and p and Q are 0 or 1. Also, 〇Sa/( a+b + c + d + e-ff + g-fh) , 〇Sb/(a + b + c + d + e + i + g + h) <1 ' 0 ^ c / ( a + b + c + d + e + i + g + h) <1, 〇Sd/(a+b (please read the back of the note first and then fill out this page)

^Paper scale speed use China National Standard (CNS) A4 Wash (2)0X29*7 mm) 71 A7 B7 + c-fd + e + fd Ministry of Economic Affairs Bureau X Credit Cooperatives Printed 1253543 V. DESCRIPTION OF THE INVENTION (40 g + h) &lt;1, 〇$e/(a+b + c 十a + e + i + g + h) &lt;1, 〇$f/(a+b + c + d + 6 + f + g ^ h ) &lt; 1 ^ ^ g / ( 3 + b + c + d + e + i + g + h) <1 ' 〇Sh/(a+b + c + d + e + i+ g + h) &lt;1; preferably 〇·1&lt; (a + c + e + i+ g + h)/(a + b + c + d-fe + f + gh) &lt;〇· 9 , better 〇· 2&lt; (a + c + e + i+ g + h) / ( a + b + c + d + e + f +. g + h ) <〇· 8 . The above resin may be substituted with an acid labile group other than the above, such as tert-butoxy, te^t-butoxycarbonyl or the like, or may form a blend with a polymer substituted with such substituents. Also. In addition to the repeating unit shown in formula (8), it can be further mixed with acrylic acid derivatives, methacrylic acid derivatives, raw spinel derivatives, anhydrous maleic acid, maleic imine, acrylonitrile, vinyl acetate, ethylene. Copolymerization such as alcohol or tetrafluoroethylene is also possible. Further, the molecular weight of the base resin is preferably 2, 〇〇0 to 1 Torr in terms of the weight average molecular weight, and the range of ruthenium is preferred. The above-mentioned resin is a known method in which a base-soluble polymer is polymerized using a specific monomer, and then an acid-labile group is introduced into the carboxyl group and/or the phenolic hydroxyl group to polymerize a monomer having an acid labile group. 0 is obtained at this time, the polymerization reaction is based on the type of initiator (or catalyst), the initial method (light, heat, radiation, plasma rays, etc.), polymerization conditions (temperature 'pressure, concentration, solvent, additives ), etc., generally use a free radical initiator such as A 1 BN to carry out the free radical copolymerization of the polymerization reaction (please read the back of the note first and then fill out this page)

This paper scale applies to China's sleepy CNS) A4 wash grid (2丨0 X 297 metric tons). 43 - 1253543 A7 ——_ B7 V. Invention description (41) Combine reaction or use ionic polymerization with a catalyst such as alkyl lithium (Anionic polymerization) and the like. These polymerization methods can be carried out as a base polymer user by a dendrimer or a network dendrimer represented by 0 or (10)-1 to (ίο)-5 in a usual manner. R Α2

R&quot;2 R,' Mine ^ Μ 14^3 R43 &gt;A7 R41〇}k (r4Vh〇UV\ !40), (Please read the back of this note and fill out this page) # R&quot; R42 Ιέ' , R4D is the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 2 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 4 1 is, for example, acid unstable. And R 4 2 is a hydrogen atom or a linear, branched or cyclic alkylaryl group of a straight, branched or cyclic alkyl group having 1 to 6 carbon atoms, which may contain an ether bond. , ester linkage 5, k + m = 5, l ^ gSl, (1 〇〇, more preferably lSg $ 5 〇. R4D alkyl, aryl, R42 alkyl, R aryl and other content and above Illustrated as the same content. Order only 43 carbon number 1 to 2 〇 or carbon number 6 to 2 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 ' ' ' ' ' ' ' ' ' ' Paper ίί: The scale applies to China National Standard (CNS) A4*l (: η〇Χ29*7 public t) -44· 1253543 V. Invention description (42 A7 B7 and '3 to 丨 is 0 or positive number 1 and b' c^d'e and ί are each not 0 at the same time. At this time 'a/(a+b) ' c/(c + d ), e/(e + &quot; (a + c + e) / (a + t) + c + ... is also a range of ..., preferably 〇 8 or less, more preferably 〇. 6 or less 'best is 〇. 5 or less. The lower limit is exceeded The positive number 'especially 〇·0 i or more' is preferably 〇. 〇5 or more, more preferably 〇·1 or more. It may be the same or different from each other. The weight average molecular weight is generally 5 〇〇 to 1 〇. , 000, 〇〇〇, preferably 1' 〇〇〇 to 1, , 〇〇〇, 0 0 0 , more preferably i, 〇◦ 〇 to 1〇〇, 0〇.〇, best 2, 〇〇〇 to 5〇, 〇〇〇. At this time, the molecular weight distribution is not particularly limited, generally M w / M n = 1 · 0 to 5 · 〇., in particular; L. 〇 to 3 · Q佳.···················································································· Employees' Corruption Cooperatives Printed V·

V---A

• A 0)- 2 0)· This paper size is applicable to the national standard (CNS &gt; ( 2丨〇 X 297 mm) -45- (Please read the back of this page and read this page again)

1253543 at -______B7 V. Description of invention (43) ν· ν

V:.AI 'Λ ♦ -3 •Α Λ v\ r\ M 篇 — » ♦ ♦ ' * ♦ / /A. ν:·Α J·♦♦ ♦ Η (Please read the notes on the back and fill out this page)

Order — 霹 —

•: A /A m Ministry of Economic Affairs Intellectual Property Bureau staff levy cooperative printing ♦r·V, /: V...*aa&quot;

:A :,Γ V a. _% γ I 1 A*· This paper scale is applicable to Chinese national standards (CNS>A4 Washing {210 X 297). 46 1253543 V. Inventions (44) A7 B7 ( In the formula, the dotted polymer chain of the following repeating unit (1 i ) is the following formula (12). Further, the number of dotted lines between A and A is not related to the number of bonds (number of repeats) of the unit 1 1 ) ) R&lt;2 R&quot;

(11) (R&lt;10)k (R40)m(H〇)nt^9 R43 Π2) (Please read the note on the back and fill out this page.) Ministry of Economic Affairs wisdom on the production bureau staff poverty alleviation cooperatives A dendrimer polymerization method of a phenol derivative, for example, in a living polymerization, a reaction of a polymerizable compound is carried out, and polymerization is carried out to obtain a dendritic polymerization of a phenol derivative. The living anionic polymerization method may be any polymerization-controlled polymerization method as long as it is a living polymerization method, for example, using the monomer and/or the body represented by (1) to carry out living anionic polymerization reaction, and to quantify the compound represented by (1 1 1 ) Forming a branching compound and adding a monomer and/or a formula of the formula (i) (1, wherein the polymerization is carried out after repeated steps, the polymer, the net branch, the compound, the net, the net method. Preferably, the formula (1 after polymerization) is reversed and the continuation component of the polymer can be repeated. This is a single polymer, which is represented by the formula 1), and then with the formula (should. Show the monomer, so that the paper size of the standard object is applicable to China National Standard (CNS) A4 Washing (2) 0X29*7 mm) -47 - Α7 Β7 Ministry of Economic Affairs Zhichu 対1 Bureau employee consumption cooperative India Purple 1253543 V' invention description (45) R42 1 CH production c I (R\^ (〇R4A)k 1 R42

Wherein, ru, r42, k, see the same meaning as the above, 'R 4 is a protecting group of a hydroxyl group, for example, a straight, spheroidal or cyclical 1st, 2nd or 3rd order of carbon number 1 to 6 An alkyl group or a trialkylalkylene group; a single bond or a C 1 to 2 0 , particularly 1 to 1 Å alkylene group, and X is a halogen atom, an aldehyde group or an alkoxycarbonyl group. Further, the above-mentioned protective base such as a known protective base is not particularly limited, and finally can be dissociated by a general method. When the living anionic polymerization is carried out, the reaction solvent is preferably a solvent such as toluene, benzene, tetrahydrofuran, dioxane or ethyl ether, and particularly preferably a polar solution such as tetrahydrofuran, dioxane or ethyl ether. The mixture of two or more kinds may be used alone or in combination. For the initiator, for example, s e c _ butyl lithium, η-butyl lithium, Cai (please read the back of the note first and then fill out this page)

This paper is used at the speed of China National Motorcycle (CMS) Α4 Washing (210X 297 mm) -48- 1253543 Α7 Β7 5, invention description (46) sodium, cumyl potassium, etc. The predetermined molecular weight ratio is mixed. 1 ο to 5 ο to 8 1 1 · For ο degrees, the temperature should be responsive to the inverse OC ο as small as 5 ο to 7 5 I. It is better to be better, and the lower example is as shown below. The shape of the identifiable remedy is the beginning of the re-enactment of the re-use of the lithium-based time base Dingzhi I points its change to use, show

S e

C Ministry of Economic Affairs Zhizhi Property Bureau employees eliminate cooperatives India Purple (Jing Xian read the back of the note and fill out this page)

This paper scales the speed of China's national standard (CMS) A4*l grid U] 〇Χ 297 public shame) · 49- 1253543 five, invention description (47) Ministry of Economic Affairs wisdom '£局' 'before workers> 『fee Cooperative printing

Benzene or basal spikes (please read the notes on the back and fill out this page)

This paper scales the speed using the Chinese National Standard (CNS) A4 pit (210X 297 mm) 1253543 V. Invention description (48 2 2 Among them, the above R 3 D ' R ^ type (1) a 1 to (1) a 3 For the acid labile group, for example, any one or two or more of 3) 1 and 2 may be used, and at least a part of the atom may be subjected to the above formula (2) - 1 , ( 2 ) (3 ) - 1 or a blend of an alkali-insoluble or poorly soluble resin having a third-stage hydrocarbon group represented by (2)-2 or a second acid-stabilizing group substituted with a substituent of a 3-stage hydrocarbon group; or, containing a carboxyl group or a phenolic hydroxyl group a base polymer which is a soluble base polymer and a carboxyl group or a hydrogen atom of a phenolic hydroxyl group. The base resin of the present invention for alkali-insoluble or poorly soluble in a photoresist material contains a carboxyl group or a phenolic hydroxyl group. a base polymer which is soluble in an aqueous alkali solution, and at least a part of a hydrogen atom of a carboxyl group or a phenolic hydroxyl group is represented by the above formula (1)-1, (1)-2 or (丄)-3. An alkali-insoluble or poorly soluble resin which is substituted with an acetal or a ketal group, and an insoluble or poorly soluble resin A carboxyl group or a phenolic hydroxyl group is a soluble base polymer in an aqueous base solution, and at least a part of the hydrogen group of the carboxyl group or the phenolic hydroxyl group is printed by the Consumer Information Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs. Read the back of the note first, then fill out the first acid-stabilized group substituted by the acetal or ketal group shown in 3), and note at least a part of the remaining hydrogen atoms. (2) an alkali-insoluble or difficult second-acid labile group substituted with a 3-stage hydrocarbon group represented by a 1, 2, (2) - 2 ' (3) - 1 or (3) - 2 or a substituent containing a 3-stage hydrocarbon group A soluble resin or the like. In this case, the ratio of the first acid labile group to the second acid labile group in the entire base resin is from 9:95 to 95:5', preferably 1〇:9〇. To 9〇:1〇, the best is 12:88188:12 0 The paper size is applicable to the Chinese national standard (〇^〉六四说格(210父29*?公袭) -51 - 1253543 A7 B7 V. Invention DESCRIPTION OF THE INVENTION (49) The photoresist material of the present invention contains (A) a base resin, (B) an organic solvent, and (C) an acid generator as essential components, preferably It is preferable to contain (D) a basic compound and (E) a dissolution inhibitor. The organic solvent of the component (B) used in the present invention may be any organic solvent which can dissolve an acid generator 'base resin, a dissolution inhibitor, and the like. The organic solvent is, for example, a ketone such as cyclohexanone or methyl 2-n-pentanone; 3-methoxybutanol, 3-methyl-3-methoxy-1-methoxy- 2-7-(73⁄4 alcohol) 1 monoethoxy-2-propanediol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monool monoethyl ether 'propylene glycol dimethyl ether, diethylene glycol di; propylene glycol monomethyl ether acetate , propylene glycol monoethyl ethate, ethyl pyruvate butyl acetate, 3-methoxy-ethoxy propionic acid acetylation, acetic acid ter ΐ butyl vinegar, monobutyl acrylate, ethylene glycol propionate Tert - butyric acid. The ratio of addition is 1 〇〇 to 2 〇, 〇〇 0 parts, preferably 5 00 parts, to 1 Ο ( (same) of the base resin. The acid generator of the component (C) is, for example, the following formula (, the azomethane derivative of the formula (17), the formula (1) The paper scale is applicable to the Chinese National Standard (CNS) A&lt;Washing (2! Ο X 297 mm) (Please fill in the page on the back of M#)

Alcohols such as oxybutanol ' 1 alcohol; esters such as ethyl acetate and ethyl dimethyl ether, such as methyl lactate, methyl lactate, and tert acetate; 〇1 to 6) _Salt 8) 乙二肟 Ministry of Economic Affairs Intellectual Property Bureau Employees Elimination Cooperatives Print Disaster 52 1253543 A7 ---- B7 V. Description of Invention (5〇) Derivative ' /5-ketosulfonic acid Derivatives, disulfonic acid derivatives, nitrobenzylsulfonic acid Si derivatives 'sulfonate derivatives, quinone imine-sulfonate derivatives, and the like. Further, an acid generator which produces decane monosulfonic acid per week is preferred. (R 3 0 ) b Μ - K - (16) (where rU is a linear, branched or _-like enthalpy of carbon number 6 to 12 aryl or carbon having 6 to 12 carbon atoms The number 7 to 12 of the aralkyl group 'M- is 镒, 铳, and K is a non-nucleophilic counter ion). An alkyl group of 3 0 R such as methyl, ethyl, propyl, butyl, cyclohexyl '2-mineoxyhexyl, ortho-alkyl, adamantyl, and the like; an aryl group such as phenyl 'P-methoxyphenyl , m-methoxyphenyl' fluorenylmethoxyphenyl, ethoxyphenyl, t-butoxyphenyl, m-tert-butoxyphenyl, and the like, oxyphenyl; 2-methylphenyl, 3 An alkylphenyl group such as -methylphenyl, 4-methylphenyl, ethylphenyl' 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl; aralkyl Base, phenethyl and the like. K non-nucleophilic counter-opposite, such as halide ion such as chloride ion or bromide ion, cycloalkyl monosulfonate, orthorane sulfonate, adamantane sulfonate, etc.; Formate, 1,1,1-trifluoroacetamidine, fluoroalkyl sulfonate such as perfluorobutane sulfonate, tosylate 'benzenesulfonate, 4-monophenylsulfonic acid Salt, 1, 2,3,4,5-pentafluoro, phenyl sulfonate, 1-naphthyl sulfonate, 2-naphthyl sulfonate, ρ-methoxy sulfonate, ΠΊ-曱 oxygen Benzobenzenesulfonate, ρ-fluorobenzenesulfonate, P-tert-butoxybenzenesulfonate, ρ-tolyloxybenzylsulfonate, p-phenoxybenzenesulfonate, p- An aryl sulfonate such as a methoxy sulfonate; an alkyl sulfonate such as a methylsulfonium salt or a butane sulfonate; and the like. This paper scales the speed of the Chinese ffi sample sample (CMS) A4 pit (2) 0X297 public education) -53 - (Please read the back of the note and fill out this page)

Order Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed A7 B7 (17) 1253543 V. Invention Description (51) n2

II R31 - S02-C-S〇2- R32 η First read η Back i Please fill in this page (in the formula, R3) ' R32 is a linear number, a branch _ or a ring of carbon number ^ to ^ 2 An alkyl group or a halogenated alkyl group, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R 3 1 , R 3 2 alkyl such as 1 〇-decyl, methyl, ethyl 'propyl, butyl, pentyl, cyclopentyl, cyclohexyl, raw spinel, adamantyl, etc.; Halogenated alkyl groups such as trifluoromethyl, 1,1,1-trifluoroethyl, 1,1,1-trichloroethyl, nonafluorobutyl, etc.; aryl groups such as phenyl, P-methoxyphenyl, M-methyl-oxyphenyl, fluorenyl-methoxyphenyl, ethoxyphenyl 'P-tert-butoxyphenyl, m-tert-butoxyphenyl, etc.; 2-methylphenyl, 3-methylphenyl, 4-monophenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, dimethylphenyl, etc. alkylphenyl; halogenated aryl Fluorophenyl, chlorophenyl ' 1 ' 2 ' 3 ' 4 , 5-pentafluorophenyl, etc.; aralkyl group such as benzyl, phenethyl and the like. R: '&lt; R35 R33- S〇2 - 〇i (18) I I π = C - C = Nis 〇 2 - R. 3 Ministry of Economic Affairs, Ministry of Finance, Printing, Co., Ltd. (wherein R 3 3, R 3 4, and R 3 5 are straight-chain, branched or cyclic alkyl or halogenated carbons of 1 to 1. An alkyl group, an aryl group or a halogenated aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms; and R34 'R35 may be bonded to each other to form a cyclic structure, and when formed into a cyclic structure, R 3 4 And R 3 5 are each a linear or branched alkyl group having 1 to 6 carbon atoms). , RU, R35 alkyl, halogenated alkyl, aryl, halogenated paper speed Chinese standard (CMS) Adit (2! ΟΧ 297 mm) 1253543 Ministry of Economic Affairs Zhichu Property Bureau employee consumption cooperative printed A7 B7 V. Description of the invention (52) The aryl group and the aralkyl group are the same as those described for R3] and R32. Further, the alkyl group of R 3 75 ' R 3 5 is as defined by the methyl group. a propyl group, specifically, for example, a decanesulfonate diphenyl iodine gun, a decanesulfonic acid (P-tert-butoxyphenyl)phenyl iodide, a p-toluenesulfonic acid diphenyl iodonium, P -toluenesulfonic acid (P-tert-butoxyphenyl)phenyliodonium, triphenylsulfonium decanesulfonate, decanesulfonic acid (p-tert-butoxyphenyl)diphenylsulfonium, decanesulfonate Acid bis(p-tert-butoxyphenyl)phenyl fluorene sulfonate tris(p-tert-butoxyphenyl) fluorene, P-toluenesulfonic acid triphenyl vegetable, ρ-decane sulfonic acid ( P-tert-butoxyphenyl)diphenylanthracene, bis(p-tert-butoxyphenyl)phenylsulfonate, tris(p-tert-butoxyphenyl)) , P - Triphenylsulfonium benzenesulfonate, P-tertenebenzenesulfonic acid (p-tert-butoxyphenyl)diphenylphosphonium, p-.toluenesulfonic acid bis(p-tert-butoxyphenyl)phenylhydrazine, Tris(p-tert-butoxyphenyl)phosphonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, trimethylsulfonium decanesulfonate, p-toluene Trimethyl sulfonium sulfonate, cyclohexanemethyl (2-carbonylcyclohexyl) fluorene, p-toluenesulfonic acid cyclohexyl (2-carbonylcyclohexyl) fluorene, decane sulfonic acid dimethylbenzene Base, p-toluenesulfonic acid dimethylphenylsulfonium, decanesulfonic acid dicyclohexylphenylphosphonium, p-toluenesulfonic acid dicyclohexylphenylphosphonium, etc.; bis(nonanesulfonyl) Azomethane, bis(phenylsulfonyl)diazomethane, bis(P-toluenesulfonyl)diazomethane, bis(xylsulfonyl)diazomethane, bis(cyclohexylsulfonyl) Diazomethane, bis(cyclopentanesulfonyl) (please read the notes on the back and fill out this page)

The paper size is 中国 China National Standard (CNS) A4 specification (210X 297 mm) .55 - 1253543 A7 B7 Ministry of Economic Affairs Zhiwu, invention description (53) Diazomethane 'bis(η-butylsulfonate) Diazomethane bis(isobutyl hydrazino)diazomethane bis(S e C-butyl fluorenyl) diazomethane, bis(η-propylsulfonyl)diazomethane , m (isopropyl sulfonyl) diazomethane, bis( ter ΐ butyl fluorenyl) azomethane, bis(η -pentylsulfonyl) diazomethane, bis (isoamyl) Sulfosyl)diazomethane, bis(S e C-pentylsulfonyl) azozoene bis (tert-pentylsulfonyl) azomethanone 1 - cyclohexylsulfonyl-1 One (tert-butylsulfonyl) diazocarbazide ' 1 -cyclohexylsulfonyl- 1 -( ie Γ t - pentylsulfonyl) diazo-methyl, 1 -t eT t-pentyl Diazomethane derivatives such as sulfonyl-1 - (tert-butylsulfonyl) diazomethane •, double-〇一( p —toluenesulfonyl) a — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — A-dicyclohexyl. ethanedioxime, bis-indolyl (P-toluenesulfonyl)- 2 3 - pentanediol ethanediazine, bis-indole-(P-toluenesulfonyl)-2 - hydrazine一1 3 5 4 pentanedione ethanedioxime, bis-indolyl (η-butanesulfonyl)-a-methyl-diethyl hydrazide-one ( π-butyl sulfonate) — a — — 乙春乙二肟一〇一( η — butanesulfonyl)- a dicyclohexylethylene dioxime, bis-indole — (η — butanesulfonyl)- 2 3 —pentanediol乙二肟's bis- 〇 1 ( η — butane sulfonyl)- 2 — methyl — 3 &gt; 4 pentylene glycol ethylene dioxime, biguanide (methanesulfonyl) one a two Methyl ethanediazine bis- 〇:-(decanesulfonyl)-α--methylglyoxime-indole (1 丄L ] 1 , J 1 trifluoro Alkyl sulfonyl) A dimethyl dimethyl hydrazine double 〇 first W Read the back i matter and then fill out this page paper size 逍 use Chinese 标准 standard (〇 ^) six 4 said grid (2] 0 / 297 · · · · · · · · · · · · · · · · ········································································································ —(Perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-indolyl (cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-benzene A) dimethyl dimethyl hydrazine, bis-indenyl (p-fluorophenyl sulfonyl)-α-dimethyl ethane sulphate, bis-o- (ρ-tert-butyl benzene sulfonate) ) α-dimethylglyoxime, bis-indolyl (xyl sulfonate), dimethyl hydrazide, bis-indolyl-(decanesulfonyl)-α-dimethyl-2-indene Ethylene dioxane derivative, 2-cyclohexylcarbonyl-2- 2 -(indolyl-toluenesulfonyl)propane ' 2 -isopropylcarbonyl-2 - (ρ-toluenesulfonyl)propane, etc. /9-one ketone Diphenyl sulphate, dicyclohexyl sylylene, etc.; two derivatives; ρ-toluenesulfonic acid 2,6-dinitrophenyl ester, hydrazine-toluenesulfonic acid 2,4 dinitrophenyl ester Phenyl sulfonate derivatives; 1, 2, 3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, 1, 2, 3 a sulfonate derivative such as tris(p-toluenesulfonyloxy)benzene; quinone imine-yl-trifluoromethanesulfonate, quinone imine-toluenesulfonate, 5-pronylene Base-2,3 -di-residue quinone imine-based-tri-n-methylsulfonic acid vinegar, 5-former-alkenyl- 2,3-dicarboxyarmine-mono-toluenesulfonate, 5-origin Wave-based group - 2 ' 3 - a residue quinone imine-based-n-butyl butyl acid oxime and the like quinone imine-yl-sulfonate derivative. Further, the acid generator may be used alone or in combination of two or more. The amount of the acid generator added is preferably from 〜 2 to 15 parts by weight of the total base resin of from 1 to 5 parts by weight, more preferably from 0.5 to 8 parts. If it is less than 0 · 2 parts, the acid production will be too low during the exposure, and there will be sensitivity and resolution (please read the back: VJL and then fill out this page)

This paper scale applies to Chinese national standards (CNS>A4 washing grid (2)0X297 mm) - 57- 1253543 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing ^ A7 B7 V. Invention description (55) The situation is higher than 2 When 0 parts are used, the transmittance of the photoresist is lowered, and the resolution is deteriorated. A compound having a diffusion rate of acid in the photoresist film is preferred. The addition of a basic compound suppresses the diffusion rate of the acid in the photoresist film, thereby improving the resolution, thereby suppressing the sensitivity change after exposure, reducing the dependence of the substrate or the environment, and improving the exposure latitude or the shape of the pattern (for example, the special opening) .5 — 2 3 2 7 0 6 , 5 - 249683 , 5 - 158239 , 5 - 2 49662 , 5 - 257282 , 5 - 289332 , 5 - 289340 , etc.). The basic compound may be, for example, a first-stage, a second-stage, or a third-order aliphatic amine, a mixed amine, an aromatic amine, or a heterocyclic amine, a nitrogen-containing compound having a carboxyl group, and a swelling-containing group. A nitrogen compound, a nitrogen-containing compound having a transbasic nitrogen-containing compound 'having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, a guanamine derivative, a quinone imide derivative, or the like. Specifically, a first stage fatty amine such as urea, methylamine, ethylamine, η-propylamine, isopropylamine, η-butylamine, isobutylamine, sec-butylamine, tert- Butylamine, amylamine, tert-pentylamine, cyclopentylamine 'hexylamine, cyclohexylamine, heptylamine, octylamine 'mercaptoamine' mercaptoamine, laurylamine, cetyl Amine, methyl diamine, ethyl diamine, tetraethylamylamine, etc.; second aliphatic amines such as dimethylamine, diethylamine 'di-n-propylamine, two Isopropylamine, di-n-butylamine 'diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine 'dicyclohexylamine, diheptanyl basic The paper recognition scale is applicable to the Chinese national standard (CNS>A4 pit (2)0Χ 297 mm) (please read the back of the &gt;± intentions and fill out this page)

-58- Ministry of Economic Affairs, Intellectual Property, Intellectual Property, Staff, Consumers, Cooperatives, Printing and Burning, 1253543 A7 B7 V. Description of Invention (56) Amine 'Dioctylamine' Dinonylamine' Didecylamine, Dilaurylamine, Dicetone Amines 'N,N-dimethylmethyldiamine, N,N-dimethylethylidenediamine' N,N-dimethyltetraethylamine, etc.; Amines such as trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine 'tri-n-butylamine' triisobutylamine, di-sec-butylamine, Tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, tridecylamine, tridecylamine, trilaurylamine, cetylamine , N,N,N / ,N z -tetramethylmethyldiamine, N,N,N ' ,N tetramethylethylidene diamine, N,N,N /,N / -tetramethyl Tetraethylamine and the like. Further, a mixed amine such as dimethylethylamine, methylethylpropylamine, pentylamine, phenethylamine, benzyldimethylamine or the like. Specific examples of the aromatic amines and the heterocyclic amines are, for example, aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline 'N., N-dimethylaniline, 2 -methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, dinitroaniline '3-nitroaniline, 4-nitroaniline, 2,4 Dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethylaniline, etc.), diphenyl(P-tolyl)amine, methyldiphenyl a base amine, a triphenylamine, a phenylene diamine, a naphthylamine, a diaminonaphthalene, a pyrrole derivative (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2, 5 - dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (such as oxazole, isoxazole, etc.), thiazole derivatives (such as thiazole, isothiazole, etc.), imidazole derivatives (such as imidazole, 4 Monomethylimidazole, 4-methyl-2- 2 (Please read the back of this page and fill out this page)

This paper music standard speed China® home standard (CNS) A4 pit (2) 0X 297 mm) -59- Ministry of Economic Affairs Intellectual Property Bureau 8 Workers Elimination Cooperatives Printing Disaster 1253543 A7 B7 V. Invention Description (57) -Benzene Pyrimidazole, etc.), pyrazole derivatives, furan derivatives, pyrroline derivatives (eg pyrroline '2-methyl-1-pyrroline, etc.) 'pyrrolidine derivatives (eg pyrrolidine 'N-methylit) Pyrrolidine, d-pyrrolidone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazopyridine derivatives, pyridinium derivatives (eg pyridine, picoline, ethylpyridine, propylpyridine, butyl) Pyridine, 4-(1-butylbenzyl)pyridine, lutidine, trimethylpyridine 'triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine' 4 Pyridine, biphenylpyridine, pentylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyrrolidone, 4-pyrrolidone, 1-A 4-yl-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc., pyridazine derivatives, Pyridine derivative, pyrazine derivative, pyrazoline derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, anthracene derivative, isoindole derivative, 1 Η .-carbazole derivatives, porphyrin derivatives, quinoline derivatives (such as porphyrins, 3-porphyrincarboxonitriles, etc.), iso-doxa derivatives, porphyrin derivatives, d-oxazoline derivatives, d|porphyrin derivative, pyridazine derivative, anthracene derivative, acridine derivative, carbazole derivative, phenanthroline derivative, acridine derivative, phenazine derivative, 1, 1 fluorene-phenanthrene A porphyrin derivative, an adenine derivative, an adenosine derivative, a guanine derivative, a guanosine derivative, a uracil derivative, a urazine derivative, or the like. Further, a nitrogen-containing compound having a carboxyl group such as aminobenzoic acid, anthraquinonecarboxylic acid, or an amino acid derivative (for example, nicotine acid, alanine, arginine, aspartic acid, decanoic acid, glycine, histidine, Isolysine, &amp; amidine leucine, leucine, methionine, phenylalanine, threonine, lysine (please read the back of the note before you fill out this page)

This paper scales the speed of China's national standard rate (CNS) eight 4 this grid (2) 0X297 public education) _ 6〇 · Ministry of Economic Affairs Intellectual Property Bureau staff levy cooperatives printing ^ 1253543 A7 __B7 V, invention description (58), 3 - An example of an aminopyridinium-2-carboxylic acid, a methoxypropylamino group, or the like; a nitrogen-containing compound having a sulfonic acid group such as 3-pyridinesulfonic acid or P-toluenesulfonic acid; A nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, and the like, for example, 2-hydroxypyridine, aminocresol, 2'4-monomorpholdiol, 3-hydrazine methanol hydride, monoethanolamine, diethanolamine, three Ethanolamine 'N-ethyldiethanolamine, N,N-diethylethanolamine, tripropanolamine '2,2/-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino group 1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyl) Ethoxy)ethyl]piperazine, piperazine ethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidone, 3-pyrrolidone-l,2-propanediol '3-pyrrolidone-l,2-propanediol, 8-hydroxy jiuronidine '3-quinacridol' 3 - tropinol' 1 I. thiol-2 Pyridineethanol, 1-azacyclopropaneethanol, N-(2-hydroxyethyl)peptide quinone imine, N-(2-hydroxyethyl)isonicotine amide, and the like. Indoleamine derivatives, for example, formamide, N-methyldecylamine, N,N-dimethyldecylamine, ethylamine N-methylacetamide, N,N-dimercaptoacetamide, Trimethyl acetamide, amylamine, and the like. The quinone imine derivatives are, for example, quinone imine, amber waking imine, maleimide and the like. Further, one or two or more kinds of basic compounds selected from the following formula (1 9 ) or ( 2 〇) may be further added. (Please read the notes on the back and fill out this page)

This paper scales with the Chinese BI standard (CNS) A4 wash (2丨0X297 mm) _ 61 · 1253543 Α7 ___ —_Β7_ V. Description of invention (59 ) CH2CH20(R41〇)sr^ CH2CH20(R42〇)tR45 (19) __j CH2CH2〇(R43〇)uR^ ! CH2CH20(R470)sR^ N-CH2CH2O(R48〇)tR50 (20) H ' (where R4]' rH' r43, r47, r48 are independent a chain-like branched or cyclic alkyl group having 1 to 2 carbon atoms, R44, R45, R46', R49 and R5D are a hydrogen atom, an alkyl group or an amine group having 1 to 2 carbon atoms, and R44 and R45. , ruler 45 and ruler 46, R44 and R46, and r45 and r46, ruler "and ruler" can be individually bonded to form a ring. S, τ 'U are each an integer from 〇 to 20. But when s, 丁, ϋ = 0 When, r45, r46, r49, r5D do not contain a hydrogen atom). Wherein R 4 ], r 4 2, R 4 3 ' r 4 7 , r 4 8 may have a carbon number of 1 to 20, preferably 1 to 1 Å, more preferably 1 to 8 carbon atoms. An alkyl group, specifically, for example, a methyl group, a fluorenyl 'n-propyl group, an extended isopropyl group, a η-butylene group, an isobutyl group, a η-amyl group, an isoamyl group Stretching the base 'extension base, stretching base, stretching cyclopentyl, stretching cyclohexyl and so on. Further, R 44, R, R 4 6 , R 4 9 and R 5 . The alkyl group is, for example, a carbon number of 1 to 20, preferably 1 to 8, more preferably a carbon number of 1 to 6, which may be linear, branched or cyclic. Specifically, for example, methyl, ethyl, η-propyl, isopropyl, monobutyl, isobutyl, tert-butyl, η-pentyl, isopentyl, hexyl, decyl, hydrazine The paper scale is speeded up by China National Standard (CNS) (2) 0Χ 297 嫠 (read the first reading of M on the back)

Ministry of Economic Affairs Zhi Chucai 1 Bureau of Staff Consumption Cooperatives printed ^ 1253543 a7 B7 V, invention description (60), lauryl alkyl 'tridecyl, cyclopentyl, cyclohexyl and so on. Further, when RH and R45, RU and RU, and R"' &gt; 5〇 form a ring, the carbon number of the ring is from 1 to 20, more preferably from 1 to 8, most preferably from 1 to 6, and more preferably The alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, may have a branch. S, T, and U are each an integer of 〇 to 20, preferably 1 to 1 Torr, and most preferably an integer of 1 to 8. The specific contents of the compounds represented by the above (1 9 ) and (20), for example, three {2-(methoxymethoxy)ethyl}amine, three {2 - (2-methoxyethoxy) B Base amine, tris(2-methoxyethoxymethoxy)ethyl}amine, tris(2-methoxyethoxy)ethyl}amine, triterpenoid 2 - (1 - Ethoxyethoxy)ethyl)amine, tris{2-(1.-ethoxypropoxy)ethyldecylamine, tris[2-indol-2-(2-hydroxyethoxy)ethoxy}B Amine, 4,7,13,.16,21,24 (Read the first note on the back and fill out this page)

, -ιτ i~V 8 8 8 \-t Cyclodiazepine II I ο 1 1 I oxyhexadesane 6 3 _-一--^ , LO 7 , 5 LO 4 , , 8 Ring 7 Dioxane Nitrogen 421 I 3 〇 1 I—i , , 〇•—I |—II , Oxygen 4 4′ -1 8 , 1 alk mw! Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing ^ β |--*· Ring Diaza 1 amine I grade heterotriazole is 1 别 5 • — 1 4 I Crown I 2 1 I Miscellaneous 0 1 1 Alkane VIII 5 Isopronamine 1 Benzene I-1 special.物等6 衍1 啶冠冠 I, -8 物1 生 I 杂 烷 烷 I I 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Alcohol, derivatized acid hydration, nitrogen, content of the base phenyl hydroxy hydroxy 01 has a base 2 B t) triyl, oxomethyl} oxymethyl b / (V \) / 1 base 2 oxet 3 lines of trioxane and abundance ( /#1* amine 1 sub-2 2 2 A paper grade speed using Chinese national standard (CMS) A4 saying grid (210X29*? mm) -63- Ministry of Economic Affairs Bureau staff consumption cooperatives, printing disasters 1253543 Λ7 Β7 5, invention description (61) oxyethoxy) methyl) ethyl amide, i-aza 丄 5 冠 1 一 5, etc. is preferred. The above basic compound may be used in an amount of from 01.01 to 2 parts by weight of the entire base resin, and more preferably from 0.1 to 1 part by weight. When the amount of addition is less than 0 · 0 1 part, the effect of the additive is not fully exerted, and when it exceeds 2 parts, the resolution or sensitivity may be lowered. The dissolution inhibitor of the (Ε) component is a molecular weight 2 which can change the dissolution 14 of the alkali imaging solution due to the action of an acid, and a compound of less than QQQ, particularly a low molecular weight phenol of 1,500 or less. Or a compound obtained by partially or completely replacing one of the carboxylic acid derivatives with an acid labile substituent. a phenol or a carboxylic acid derivative of a molecular star of 1,500 or less, such as 4 '4\-(1 -methylethylidene) bisphenol' ['1,1/diphenyl- 4,4 Monohydric alcohol] 2, 2 / - methyl bis[4-methylphenyl], 4,4 bis (4 &lt; hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1, 1, 1 -3 (4 &lt;~hydroxyphenyl)ethane, 1,1,2, di(4-hydroxyphenyl)ethane, phenolphthalein, thymol, 3,3,5'5, -four Fluorine [(工,工/一乙phenyl)-4,4^-diol]'4'4^~[2,2,2-trifluoro-l-(trifluoromethyl)ethylidene] Phenol, 4,4/methyl-bis[2-fluorophenol], 2,2/extension methyl bis[4-fluorophenylbenzene], 4'4&lt;-iso-sub-diyl bis[2~fluoro Phenol] 'Cyclohexylylene bis[2-fluorophenol], 4, ~[(4-fluorophenyl) This paper scales the appropriate Chinese national sample (CNS>Α4 wash grid (2)〇χ29*? ^) - -64 ^ (Please read the notes on the back and fill out this page)

1253543 A7 ________B7_ V. INSTRUCTIONS (62) Methyl]bis[2-fluorophenol], 4,4/methyl-bis[2,6-difluorophenol], 2,6/one pair [( 2 monohydroxy-5-fluorophenyl)methyl]-tetrafluorophenol, 2,6--bis[(4-hydroxy-3-trifluorophenyl)methyl]-tetrafluorophenol, 2 , 4 bis [(3-hydroxy-4-hydroxyphenyl)methyl]- 6-methylphenol, etc., and the acid-labile substituent is, for example, the same as the above. The above-mentioned addition amount is preferably from 1 to 对 for the base resin i 〇 ,, and preferably from 〇 to 5 parts. In the photoresist of the present invention, any conventional component other than the above-mentioned components may be added as a surfactant for the purpose of improving coatability. Further, the amount of the optional component added is a general addition amount within a range not impairing the effects of the present invention. Among them, the surfactant is preferably nonionic, and examples thereof include perfluoroalkyl polyoxyacetylene alcohol, fluorinated alkyl ester 'perfluoroalkylamine oxide, and fluorine-containing organic oxalate compound. For example, Fleet "FC - 4 3 0", "FC - 4 3 1" (both Sumitomo 3 Corporation), Shaflon "S - 141" - "S-145", "S - 38lj, rS - The speed of this paper is speeded up by China National Standard (CNS) A4 (2丨0χΜ7 public t) - 65 - (Please read the back of the note and fill out this page)

1 work J ί 中, ο金 1 J 1 its } 4 big 7 7Χ. System 1 is, ^17 Γ, etc. 5 are all one, etc., D (F 1 J ) Μ Γ J Γ F 2 system 3 but 1 , r 9 Siuni 5 J ο 公住优 4 1 JI industry ί ,一5 3 ο 工 J } s 1 7 7^〇D 8 1 | 化3 司Γ | | X 越四公, FF Γ 信一子J Γ 、 , for C nitrate 3 fluorine, } all F Xu 格J system ί r is 4 US 2 Division J special are I, 7 male 3 Lai cs } 1 ink 9 fluorine JD system oil ο for 3 Γ Division F this one Q0, public r day ο good 3 J industry 'big 7 Compared with the Intellectual Property Office of the Ministry of Finance, the Consumers' Credit Cooperatives are printed « A7 B7 Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Association, Co., Ltd. Printed. 1253543 V. Invention Description (63) "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. . The method of forming the pattern by using the photoresist material of the present invention may be carried out by using a well-known etching enamel brush technique, for example, on a Wi-' square-shaped substrate, and coating the thickness Q · ^ to 1 by spin coating. 〇 m m film, put it on a hot plate or oven in the range of 6 〇 to 2 ' ' 1 至 to 60 minutes, preferably 8 〇 to 15 〇 ° ° 'The hot plate is 3 0 seconds to 5 minutes 'The oven is preheated in the range of 5 minutes to 30 minutes. The second step is to form a pattern with an electron beam at an exposure of about 1 to 2 〇〇MC, preferably 2 to 5 0 // C, and 60 to 200 ° C on a hot plate or a hot oven. 1 Torr to 60 minutes, preferably 8 Torr to 150 ° C, and irradiated with hot water (PEB) after 30 seconds to 5 minutes on the hot plate. Thereafter, a developing solution of an alkaline aqueous solution such as 1 to 5%, preferably 2 to 3% of tetramethylammonium hydroxide (butyl HA) is used, for 10 seconds to 3 minutes, preferably 3 0 The target pattern is formed on the substrate by a usual development method such as a dip method, a peddle method, or a spray method in seconds to 2 minutes. [Effects of the Invention] The photoresist material of the present invention has excellent post-exposure vacuum placement stability in electron beam exposure processing, and the curl on the Cr substrate is also small, and has excellent sensitivity, resolution, plasma etching. patience. Therefore, the photoresist material of the present invention is extremely suitable as a fine pattern forming material for use as a mask substrate processing based on the above characteristics. {Please read the notes on the back and fill out this page)

This paper scale applies to the Chinese ffi standard (CNS) grid (2丨0X297 mm). ββ 1253543 Λ7 __ B7 V. Description of invention (64) [Examples] (Please read the notes on the back and fill out this page) The invention will be more specifically described by way of examples and comparative examples, but the invention is not limited by the following examples. (1) The photoresist solution was prepared by using the polymer 1 to 16 'acid generator (PAG 1 ' 2 ), the dissolution inhibitor (DRI 1 ), the basic compound, and the like shown below, and the weight ratio was 1: 1 propylene glycol monomethyl ether acetate (PGMEA) and ethyl lactate (EL) with a fluorine-containing surfactant f C-430 in a ratio of 1 〇〇 PP m to 300 ppm solvent (Sumitomo 3M The 800 parts by weight of the solvent produced by the company was thoroughly mixed, and then filtered with a high density polyethylene filter having a pore diameter of 0 · 1 μm to prepare a photoresist solution. (2) Describe the Ministry of Economic Affairs, the Ministry of Property, the staff of the Poverty Alleviation Cooperative, and use the CF S - 4E S manufactured by Shibaura Co., Ltd. on a 6-inch quartz quartz wafer to form a C 膜 film by sputtering. On a 〇nm thick substrate, Zhou Clinton M ark 5 (manufactured by Tokyo Electronics Co., Ltd.) spin-coated a photoresist thereon, and then preheated it with a hot plate at 100 ° C for 90 seconds. 5 0. 0 nm photoresist film. Further, the E B drawing device manufactured by Takino Rick Co., Ltd. was drawn in a vacuum chamber with a ΗV voltage of 3 0 k e V and a beam current of 1.1A. After the description, use Clinton Mark 5 (Tokyo Electronics Co., Ltd. This paper scale applies Chinese National Standard (CNS) A4*t (2) 0X 297 mm) · 67 - 1253543 V. Invention Description (66 A7 B7 Polymerization -] m:n = 0.35:0.65 M w 1 1 000 M w/Mn 1 . 1 0 Polymer-2 m:n:p = 0.20:0.12:0.68 Mw]l,000 Mw/Mnl.10 Polymerization -3 m:n:p = 0.35:0.05:0.6 Mwl6,000 Mw/Mnl.40 Polymer-4 Ministry of Economic Affairs Intellectual Property Bureau Staff Expenses Cooperatives

(Please fill in the page on the back of M# first) m : n = 0.3 : 0.7 M w 1 1 5 0 0 0 M w / Μ n 1 . 1 0 This paper music standard speed Chinese national standard (CNS) A4 Washing (2! OX 29*7 mm) 1253543 Λ7 B7 Ministry of Economic Affairs Zhichu Property Bureau Staff Consumption Cooperatives Printing Disaster V. Inventions (67)

Polymer 4 m : η = 0.3 :0.7 Mwll,000 Mw/Mnl.10 Polymer m : η = Ο . 3 : 0.7 Mwll,000 Mw/Mnl.lO Polymer-7 Branch 3 a : b = Ο 3 : Ο . 7 Mwl 1,000 Mw/Mnl.20 Polymer m : η = 0.3 : 0.7 Mwl 3,000 Mw/Mnl.68 The paper scale applies to China National Standard (CNS) A4*Jt (2) Ο X 297 mm) _ 70 - (Please read the notes on the back and fill out this page)

Order φ, 1253543 a7 B7 V. Description of invention (68)

Polymer -9 m: η = 0.26: 0.74 Mwl 3,000 Mw / Mnl. 73 Polymer _ 1 0 m: n: p = 0.25: 0.07: 0.68 Mwl 3,000 Mw / Mnl. 77 Polymer - 1 1 m: n:p = 0.25:0.05:0.7 Mwl5?000 Mw/Mnl.92

Η 〇 Polymer-1 2 m : n = 0.3 : 0.7 Mwl 3,000 Mw/Mnl.68 Polymer-1 3 m : n = 0.3 : 0.7 Mw 1 2,000 M w/Mn 1 .60 (Please read the back note first) Please fill out this page again).

The paper is scaled to the Chinese National Standard (CNS) A4 (6) 〇X29*7 mm) 1253543 A7 B? V. Invention Description)

Polymer · 1 4 m : η = Θτ3 rOv

〇

OH

Ο

OH

Mwl 2,000 Mw/Mnl .63 Polymer-1 5 m : n = 0.4 : 0.6 Mwl 3,000 Mw/Mnl.70 Polymer-1 6 m:n:p = 0.3:0.1:0.6 Mwl 3,000 Mw/Mnl .75

〇 IO3S- ’0

PAG1 Ministry of Economic Affairs Zhichu Property Bureau employee consumption cooperatives printed disaster,

k

PAG2 -o again.

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NT o again. - DRI1 (please read the notes on the back and fill out this page)

〇, i

TMMEA This paper scale applies to China National Standard (CMS) A4*t (2丨0X 297 mm)· 72 ·

Set I Patent Specification Chinese Enhanced Chemical Positive Photoresist Material Invention New Name English

Chemically amplified positive resist composition Name Nationality (1) 畠山润(1) Nakaguro-mura, Nakaguro-gun, Nakaguro-mura, Niigata Prefecture, Japan, 2nd, West Fukushima, Erlang, Japan - Name of the inventor's residence and residence (name) (1) Shin-Etsu Chemical Industry Co., Ltd. Shin-Etsu Chemical Industry Co., Ltd. Ministry of Economics, Intellectual Property Office, Completion of Consumer Cooperatives, Printing of Nationality III, Applicant's Residence, Residence (Company) Name of Representative (1) Japan (1) Otemachi, Chiyoda-ku, Tokyo, Japan二丁目六番一号 (1) Jinchuan Chihiro This paper scale applies China National Standard (CNS) A4 specification (2:0X:97 mm) ab!2&gt;;p_7553 patent application Zhongwenbei Mingshu revision page kl Republic of China Amendment, August 31, 1994 -....::-ID, _ ___ D / V. Description of the invention (12) The acetal or ketal group shown in 3 is substituted with the base containing the first acid labile group. ―Soluble---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- a solution of a soluble base polymer, and At least a portion of a hydrogen atom of a phenolic hydroxyl group or a phenolic hydroxyl group is a substituent having a hydrocarbon group of the formula 3 represented by the above formula (2)-1 or (2)-2'(3)-1 or (3)-2 The substituted alkali-insoluble or poorly soluble resin containing a second acid labile group. In the above-mentioned photoresist material, the base resin is a base polymer which is soluble in a base aqueous solution having a carboxyl group or a phenolic hydroxyl group, and at least a part of the hydrogen atom of the carboxyl group or the phenolic group is subjected to The first acid-labile group substituted by the acetal or ketal group represented by the formula (1)-1, (1)-2 or (1)-3, and at least one of the remaining hydrogen atoms The second part of the formula (2) -1 or (2) - 2, (3)-1 or (3) - . - 2 is substituted with a substituent of a 3-stage hydrocarbon group or a substituent containing a 3-stage hydrocarbon group. An alkali-insoluble or poorly soluble resin containing at least two acid-labile groups of an acid-labile group may also be used. Among them, the base polymer soluble in the aqueous alkali solution is preferably one or two or more kinds of the following units, for example. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the Consumer Cooperatives. This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X297 mm).

A7 B7 V. Description of invention (65)

The heating plate is 1 1 〇.热, hot baking at 90 seconds (PEB-post-one-mixing development, to produce a positive pattern. Also 'put the sample placed in the vacuum chamber in the drawing device for 24 hours after painting> same The development was carried out by PEB. The measurement of the pattern size was carried out by using SE Μ, S - 7 2 0 0 (manufactured by Hitachi, Ltd.), and the pattern obtained was evaluated according to the following method. First, the evaluation was made by 0·8. Exposure amount of //mL/S, and define it as the most appropriate exposure amount (Eopt). Cut the wafer and observe the cross-sectional shape of the photoresist when the most appropriate exposure amount is measured. Measure the size of the curl. Then measure the vacuum. The dimensions of the sample in the sample and the sample not placed in a vacuum are shown in Tables 1 and 2. I---.--&quot;---cloth----:--- (Please read the notes on the back and fill out this page) Φ Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperative Printed This paper scale applies to China National Standard (CNS) A4 Specification (210X297 mm) -68- 1253543 A7 B7 Ministry of Economics Property Bureau employee consumption cooperative printing 5, invention description (7〇) [Table 1] [Examples Polymer (parts by weight) Acid generator (parts by weight) Test (parts by weight) Dissolution inhibitor (parts by weight) Sensitivity (μ〇 crimp (nm) Vacuum PED (nm) Polymer-1 (15) Polymer-8 ( 85) PAG1 (4) Triethanolamine (0.1) - 7 10 +10 Polymer_2 (20) Polymer-8 (80) PAG1 (4) Triethanolamine (0.1) - 6 15 +6 Polymer-3 (17) Polymer - 8(73) PAG1 (4) Triethanolamine (0.1) - 6.5 10 +5 Polymer-4 (20) Polymer-8 (80) PAG1 (4) Triethanolamine (0.1) - 8 14 -6 Polymer-5 (20) Polymerization -8(80) PAG1 (4) Triethanolamine (0.1) - 8.5 16 -7 Polymer-6(30) Polymer-8(70) PAG1 (4) Triethanolamine (0.1) - 9.0 18 40 Polymer-7 (15) Polymer 8 (85) PAG1 (4) Triethanolamine (0.1) - 7.0 10 +8 Polymer-3 (20) Polymer-9 (80) PAG1 (4) Triethanolamine (0.1) - 6 8 -5 Polymer -10 (100 PAG1 (4) Triethanolamine (0.01) • 7 12 +12 Polymer-5(10) Polymer-11(90) PAG1 (4) Triethanolamine (0.1) - 6 10 +6 Polymer-5(10) Polymer 41 ( 90) PAG1 (4) TMMEA (0.2) - 7 8 +5 Polymer _5(10) Polymer-11(90) PAG2 (4) Triethanolamine (0.1) - 2 15 +16 Polymer-5(25) Rhyme 75) PAG1 (4) Triethanolamine (0.1) - 8 20 +5 Polymer-5(25) Polymer-13(75) PAG1 (4) Triethanolamine (0.1) - 6 10 +5 Polymer-5(25) Polymer-14(75) PAG1 (4) Triethanolamine (0.1) - 7 13 +17 Polymer-5(25) Polymer-14(75) PAG1 (4) Triethanolamine (0.1) DR11 6 15 +16 Note: Vacuum PED: After exposure, it is placed under vacuum and then re-developed. (Please read the notes on the back and fill out this page.) This paper size applies to the national standard (CNS) A4 specification (210 X 297 mm) -73- Φ- 5 ? 5 2 years B7 Ministry of Economic Affairs Intellectual Property Bureau Employees' Consumption Cooperatives Printing 5, Inventions (71) [Table 2] [Comparative Example] - Dissolution inhibitor (parts by weight) Bo rffr Acre (parts by weight) (1 part by weight) (parts by weight) (β〇fEfml (nm) (nm) Polymer-1 (100) PAG1 (4) Triethanolamine (0.1) :— 6 10 +123 Polymer-2(100) PAG1 (4) Triethanolamine (0.1) — 6.5 13 +85 Polymer-3(100) PAG1 (4) Triethanolamine (0.1) — 6.5 8 +88 Polymer-4(100) PAG1 (4) Triethanolamine (0.1) — 8 12 +55 Polymer-5(100) PAG1 (4) Triethanolamine ( 0.1) — 8 12 +40 Polymer-6(100) PAG1 (4) Triethanolamine (0.1) — 8 16 +44 Polymer-7(20) PAG1 (4) Triethanolamine (0.1) — 7 10 +126 Polymer-8 ( 100) PAG1 (4) Triethanolamine (0.1) — 6.5 18 -42 Polymer-9(100) PAG1 (4) Triethanolamine (0.1) — 6 13 -77 Polymer-11(100) PAG1 (4) Triethanolamine (0.1) — 8 18 -25 Rhyme 100) PAG1 (4) Triethanolamine (0.1) — 8 24 -30 Polymer-13(100) PAG1 (4) Triethanolamine (0.1) — 7 15 -33 Polymer-14(100) PAG1 (4) Triethanolamine (0.1) — 7 14 -43 Polymer-15(100) PAG1 (4) Triethanolamine (0.1) — 16 55 +10 Polymer-16(100) PAG1 (4) Triethanolamine (0.1) 13 48 -16 Note: Vacuum PED: After exposure, The size placed under vacuum and then developed. This paper size applies to the Chinese National Standard (CNS) A4 specification (210&gt;&lt;297 mm) (please read the notes on the back and fill out this page) -74-

Claims (1)

12) _______* A8 B8 C8 D8 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperation du printing Sixth, the scope of application for patents 90 1 1 75 53 patent application Chinese patent application scope amendments December 26, 1994 amendments 1 · A chemical line positive resistive material for electron beam exposure, which contains 1 Or two or more kinds of base polymers having a carboxyl group or a phenolic hydroxyl group which are soluble in a base aqueous solution selected from the following units (A) and having a carboxyl group or a phenolic hydroxyl group At least a part of the atom is a reinforced chemical positive resist material which is introduced into an alkali-insoluble or poorly soluble resin of an acid labile group, and the above resin contains at least two kinds of acid labile groups, one of which is an acid labile group. The acetal or ketal group represented by the formula (I - 1 ) to (I - 3 1 ) or (6) - 1 to (6) - 2 9 is the following, and the other acid labile group is the following formula (4) a tertiary alkyl group as shown in 1 to (4)-18; further, in all of the base resins, the ratio of the first acid labile group to the second acid labile group is 5: 9 5 9 5 : 5 ; [Unit A] 0 (wherein chain, branched or cyclic alkyl or fluorinated alkyl; x is 1 to 4, y is 1 To the integer of 3) This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) binding (please read the back note first and then fill in this page) 1253543 A8 B8 C8 D8 VI. Patent application scope CH2=CH-OCH2CH2〇—Η och2ch2o-ch=ch2 (Μ) CH2=CH-OCH2CH2〇\ /och2ch2〇-ch=ch2 V/ o (1-2) ch2=ch-och2ch2o hr och2ch2o-ch=ch2 ( 1-3) CH2=CH-0CH2CH20 —0CH2CH20-CH=CH2 (1-4) ch2=ch-och2ch2o —/&quot;Λ—och2ch2o-ch=ch2 million (4) (Please read the notes on the back and fill out this page) The Intellectual Property Office of the Ministry of Economic Affairs, the Intellectual Property Office, and the Consumer Cooperatives Printed on the paper scale applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -2 - 1253543 Patent application scope 8 8 8 8 ABCD CH2=CH-0CH2CH20— OCH2CH2OCH=CH2 (卜6) CH2=CH-〇CH2CH2〇OCH2CH2〇-CH=CH2 (Bu 7) ch2=ch-och2ch2o—C^1^I ch3 och2ch2o-ch=ch2 (Bu 8) (Please read the notes on the back first) Fill in this page) CH2=CH-0CH2CH20 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed och2ch2o-ch=ch2 och2ch2o-ch=ch2 ch3 I 0 CH2=CH-0CH2CH20—^y~OCH2CH20-CH=CH2 CH. (1-10) This paper scale applies to China Standard (CNS) A4 specification (210X 297 mm) 1253543 A8 B8 C8 D8 &gt; Patent application scope ch2=ch«och2ch2o 〇ch2ch2o-ch=ch2 (M1) ch2=ch-och2ch2o och2ch2o-ch=ch2 (M2) Ch3 CH2=CH-0-CH2〇 —&lt;N&gt;—C —〇CH2〇-CH=CH2 (1-13) (Please read the notes on the back and fill out this page) (M4) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed ch3 ch2=ch-.〇c-o-ch-ch2 CH3 • Sichuan, eight (M5) N OCH2CH2O-C H=CH2 H This paper scale applies to China National Standard (CNS) A4 size (210X 297 mm) _ 4 - 1253543 A8 B8 C8 D8 VI. Patent application scope 0Η2~0Η-Ο —0-CH=CH2 (1-16) ch2=ch-o aCH=CH2 (1-17) CH2=CH”0 aCH=CH2 (M8) ch2=ch-o^-s-^ o-ch=ch2 (1-19) ---------· Ir (please read the notes on the back and fill out this page) 〇CH2=CH-0 ——S —— O-CH^CH- 〇(卜20) Order 4 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print this paper The scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5-1253543 A8 B8 C8 D8 VI. Patent application scope CH2=CH-0 0«CH=CH, (1-21) CH2=CH-0 O-ch=ch2 (I-22) (Please read the notes on the back and fill out this page) O-ch=ch2 (I-23) (Bu 24) Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed Paper Size Applicable to China National Standard (cns) A4 Specification (21 ox297 mm) -6 - 1253543 A8 B8 C8 D8 7T, apply for a patent dry circumference ch2=ch-o 〇-ch=ch2 (1-25) H3c 0-CH=CH〇 CH2==CH-0 (Bu 26) (1-27) ------K---•Installation I _-----booking ------ (Please read the notes on the back and fill out this page.) Ministry of Economic Affairs Intellectual Property Office staff Consumer Cooperatives Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) 1253543 A8 B8 C8 D8 Patent Application Range CH2=CH*0 CH, ch2=ch-o—/ Vch2chchch2-^ ch3 0-CH=CH2 o - ch=ch2 (1-28) ch2=ch-o ch2=ch-o , o-ch=ch2 (1-29) ch3 ch. -o-ch=ch2 ‘o-ch=ch2 ch3 ch3 (1-30) (Please read the notes on the back and fill out this page) och=ch2och=ch2och=ch2 ch3 ch2=ch-o 〇-ch=ch2 (1-31) Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -8- 1253543 A8 B8 C8 D8 VI. Application Patent Range-CH2&quot;*〇一CH3 - CH2-〇"CH2-CH3 -CH2—0-(^^2)2—CH3 (6)-1 (6)-2 (6)-3 -CH2-〇- (CH2)3-〇H〇CH3 -CH2-〇-CH-CH3 2 Ηc H3 3-C3 HI Η CICIC (6)-4 (6)-5 6 (6)- CH〇CH3 仁〇- ch3 (6 ) -7 CH2 —CH-&quot;〇—1 一〇-ch3 (6)-8 3 2 Η Hc!c— cl H3 CH )-9 (6) (Please read the notes on the back and fill out this page) Ch3 ?h3 ch2 CH—〇«CH2~CH3 —CH—〇-CH2-CH〇H3 CH box H2 h ^ 3 2 I Η H 4 Cl(ClCH , 11 (6)-10 (6H1 2 )-1 CH, Ch3 —CH-Oi 〇_(CH2)2 - CH3 (6)-13 CH2 -CH—〇(CH2)2-CH3 (6)-14 ch3 (?h2)2 -CH-O-(CH2)2, CH3 (6)-15 •d· Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 1253543 A8 B8 C8 D8 VI. Patent application scope ch3 Ch3 ch3 ch 3 CH_〇——CH^-〇—/ I—C-OCHi ”—〇〇-ch2 - chk ] ch3 ch3 (6)-16 (6)-17 (6)-18 (6)-19 ch3 -CH-^》- u ch3 (6)-20 (6)-21 (6)-22 (6)-23 -Ο -0 Xo^P 々p (6)-24 (6)-25 (6) -26 (6)-27 (6)-28 (6)-29 ---.-------• Install Ir (please read the notes on the back and fill out this page), 11 4 Ministry of Economics Property Bureau Staff Consumer Cooperatives Printed Paper Size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -10- 1253543 A8 B8 C8 D8 Patent Application Scope R10 R11 R10 , (min. 1 (min. 2 (4)-3 R10 〇11) r1〇 „ R Rn (4)-7 (minute 5 (4)-6 (minute 4 R 13 Ο (4)-12 ¥ (4)-13 (4)-14 r) I) I·) I. ---,---.--------, 玎------0 (Please read the notes on the back and fill out this page) (4) -15 (4)-16 (Sub-17 (4)-18 Printed by the Consumers' Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs (where R1Q is a linear or branched chain of 1 to 8 carbon atoms of the same or different species) a cyclic alkyl group, or an aryl group having 6 to 20 carbon atoms, R11 and R13 being a hydrogen atom, or a linear, branched or cyclic alkyl group having a carbon number of 1 to 20' R12 is a carbon number An aryl group of 6 to 20%. 2) A chemically reinforced iridium resistive material for electron beam exposure according to claim 1 which contains a carboxyl group or a phenolic hydroxyl group which is soluble in an aqueous alkali solution. The paper size of one or more selected in the unit (A) is applicable to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) -11 - 1253543 A8 B8 C8 D8 VI. Patent application base polymerization And an acid-labile group-containing base substituted with at least one hydrogen atom of the carboxyl group or the phenolic hydroxyl group (I -τγτ^ττ^^3 1 ) to the acetal group represented by (6) - 29 Insoluble or poorly soluble resin, with, having a carboxyl group or The phenolic hydroxyl group is a soluble base polymer to the aqueous alkali solution, and at least a part of the hydrogen atom of the carboxyl group or the phenolic hydroxyl group is not contained in the above formula (4)-1 to (4)-18. An insoluble or poorly soluble resin containing an acid labile group substituted with a sulfhydryl z substituent of the third order. 3 · A chemically positive photoresist material for electron beam exposure according to the first application of the patent scope, a part of a hydrogen atom containing one or more base polymers selected from the unit (A) and having a carboxyl group or a phenolic hydroxyl group, and having a carboxyl group or a phenolic hydroxyl group, An acid labile group substituted with an acetal group represented by the above formula (I-1) to (I-31) or (6)-1 to (6)- 2 9 and having at least one of the remaining hydrogen atoms In part, the insoluble or poorly soluble resin containing an acid labile group substituted with a substituent of the alkyl group represented by the formula (4)-1 to (4) -1 8 is as described above. The photoresist material of the first, second or third patent range, ^ contains organic solvents and acid generators. 5 · If the scope of patent application 1, 2 or 3 of the photoresist materials, _ 尙 contains basic compounds. 6 · If the photoresist material of the scope of claim 1, 2 or 3, _ 尙 contains dissolution inhibitors. ' This paper scale applies to China Standard (CNS) A4 specification (210X297 mm): ' -12- m 1^1 —ϋ Α —ϋ -Λ - HI m ·ϋι n (Please read the note on the back and fill out this page), 1T d Economy Ministry of Intellectual Property Bureau employee consumption cooperative printing